Novel separators for electrochemical systems

Abstract

The present application provides novel separators for electrochemical systems. Separator systems for electrochemical systems are provided that provide electronic, mechanical, and chemical properties useful for a variety of applications, including electrochemical storage and conversion. The disclosed separators include multilayer, porous geometries that support excellent ion transfer characteristics, provide a barrier against dendritic crystal induced mechanical failures, shorts, or heat dissipation, or provide improved electrode conductivity and improved electric field uniformity. The separators disclosed include composite solid electrolytes having a support web or fiber system that provide solid electrolyte hardness and safety as well as toughness and long life of the support web or fiber, which are required for thin solid electrolytes that do not create pinholes or cracks resulting from operations.

Description

[0001] This application is a divisional application of an application filed on January 10, 2013, with application number 201910082587.8 and invention name “Novel separator for electrochemical systems”.

[0002] The application with the application date of January 10, 2013, application number of 201910082587.8, and invention name of “Novel separator for electrochemical system” is a divisional application of the application with the application date of January 10, 2013, application number of 201380030525.3, and invention name of “Novel separator for electrochemical system”. CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of and priority to U.S. Non-Provisional Application No. 13 / 545,683, filed on July 10, 2012, which claims the benefit of and priority to U.S. Provisional Application Nos. 61 / 506,489, filed on July 11, 2011, and 61 / 622,371, filed on April 10, 2012, and PCT International Application No. PCT / US12 / 46067, filed on July 10, 2012, which claims the benefit of and priority to No. 61 / 677,306, filed on July 30, 2012, and U.S. Provisional Application No. 61 / 679,584, filed on August 3, 2012, all of which are hereby incorporated by reference in their entireties to the extent not inconsistent with this specification. background

[0004] Over the past several decades, revolutionary advances have been made in electrochemical storage and conversion devices, expanding the capabilities of these systems in a variety of fields, including portable electronic devices, aerospace and spacecraft technology, passenger vehicles, and biomedical instrumentation. Current state-of-the-art electrochemical storage and conversion devices have design and performance attributes that are specifically designed to provide compatibility with a diverse range of application requirements and operating environments. For example, advanced electrochemical storage systems have been developed that span the range from high energy density batteries exhibiting very low self-discharge rates and high discharge reliability for implantable medical devices to inexpensive, lightweight rechargeable batteries that provide long operating times for a variety of portable electronic devices to high capacity batteries for military and aerospace applications that can provide very high discharge rates in short periods of time.

[0005] Despite the development and widespread adoption of this diverse array of advanced electrochemical storage and conversion systems, considerable pressure continues to stimulate research to extend the functionality of these systems, thereby enabling a wider range of device applications. The large growth in the demand for high-power portable electronics, for example, has created great interest in developing safe, lightweight primary and secondary batteries that provide higher energy density. In addition, the demand for miniaturization in the field of consumer electronic devices and instruments continues to stimulate research into novel designs and material strategies for reducing the size, mass, and form factor of high-performance batteries. In addition, continued developments in the field of electric vehicles and aerospace design also create a need for mechanically robust high-reliability high-energy-density and high-power-density batteries that can have good device performance within a useful range of operating environments.

[0006] Many recent advances in electrochemical storage and conversion technologies are directly attributed to the discovery and integration of new materials for battery components. Lithium battery technology, for example, continues to develop rapidly due, at least in part, to the discovery of novel electrodes and electrolyte materials for these systems. The element lithium has a unique combination of properties that makes it attractive for use in electrochemical cells. First, it is the lightest metal in the periodic table with an atomic mass of 6.94 AMU. Second, lithium has a very low electrochemical oxidation / reduction potential (i.e., -3.045 V relative to NHE (standard hydrogen reference electrode)). This unique combination of properties enables lithium-based electrochemical cells to have very high specific capacity. The latest lithium-ion secondary batteries provide excellent charge-discharge characteristics, and are therefore also widely used as power sources in portable electronic devices such as mobile phones and portable computers. US Patent Nos. 6,852,446, 6,306,540, 6,489,055, and "Lithium Batteries Science and Technology," edited by Gholam-Abbas Nazri and Gianfranceo Pistoia, Kluer Academic Publishers, 2004, which are hereby incorporated by reference in their entirety, relate to lithium and lithium-ion battery systems.

[0007] Advances in electrode materials, electrolyte compositions, and device geometries continue to support further development of Li-based electrochemical systems. For example, U.S. Patent Application Publication No. US2012 / 0077095, published on March 29, 2012, and International Patent Application Publication No. WO 2012 / 034042, published on March 15, 2012, disclose three-dimensional electrode array structures for electrochemical systems including lithium batteries.

[0008] Despite considerable progress, practical challenges remain associated with the continued development of Li-based electrochemical systems. Considerable problems, for example, involve dendrite formation in primary and secondary lithium and lithium-ion batteries. It is generally known that Li deposition in many electrolytes is highly dendritic, which makes these systems susceptible to problems involving short circuits, mechanical failures, and thermal runaway. Safety concerns related to dendrite formation are currently an obstacle to the implementation of metallic Li anodes in rechargeable systems. Many strategies have been implemented to address safety issues related to dendrite formation, particularly in the context of secondary batteries, including the development of non-lithium anodes and internal safety systems that can monitor problems related to dendrite formation in real time.

[0009] As generally recognized from the foregoing, there is currently a need for electrochemical systems such as lithium-based or alkali-based batteries, flow batteries, supercapacitors, and fuel cells that exhibit electrochemical properties useful for a variety of applications. Specifically, there is a need for lithium electrochemical systems that can have good electrochemical performance and a high degree of versatility for primary lithium-based batteries and secondary lithium-based batteries. Overview

[0010] In one aspect, the present invention provides separator systems for electrochemical systems that provide electronic, mechanical, and chemical properties useful for various electrochemical storage and conversion applications. The separator systems of some embodiments provide, for example, structural, physical, and electrostatic properties useful for preventing catastrophic failures in electrochemical cells and for improving performance such as cycle life and energy and power. One series of examples are separators for managing and controlling dendrite formation in metal-based batteries such as lithium-based, alkali-based, zinc-based, and lead-based batteries. In an embodiment, for example, the separator system of the present invention has a multilayer, porous geometry that supports excellent ion transfer properties while providing an effective barrier to prevent mechanical failure, electronic internal short circuits, and / or thermal runaway caused by dendrites. Another series of examples are multilayer separators consisting of several porous / perforated layers and an impermeable yet ion-selective conductive membrane, wherein the porous layer provides an effective barrier to prevent internal short circuit failures such as dendrite short circuit failures and / or thermal runaway; and the membrane layer provides an effective barrier to separate the electrolyte adjacent to the anode from the electrolyte adjacent to the cathode, which prevents contamination of either the electrode and its surface and its electrolyte, and thereby improves the performance of the battery such as energy, power and life cycle; this is particularly useful in metal-air and liquid flow batteries and semi-solid batteries, some examples being lithium-air, lithium-water and zinc-air batteries.

[0011] In an embodiment, the present invention provides a separator system for an electrochemical system, comprising: (i) a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; and (ii) a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern; the second pattern having an offset alignment relative to the first pattern, such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap by less than or equal to 20% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer; wherein the first high mechanical strength layer and the second high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer and the second high mechanical strength layer can be transferred through the first high mechanical strength layer and the second high mechanical strength layer. In an embodiment, for example, the first high mechanical strength layer and the second high mechanical strength layer are not in direct physical contact with each other. In an embodiment of this aspect, the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap by less than or equal to 10% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer. In an embodiment, for example, the separator system of the present invention also includes one or more electrolytes disposed between the first high mechanical strength layer and the second high mechanical strength layer and optionally in contact with the first high mechanical strength layer, the second high mechanical strength layer, or both, wherein the first high mechanical strength layer and the second high mechanical strength layer are ion conductive and optionally allow transfer of electrolytes of the electrochemical system.

[0012] In an embodiment, the present invention provides a separator system for an electrochemical system, comprising: (i) a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; (ii) a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern; the second pattern having an offset alignment relative to the first pattern such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap by less than or equal to 20% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer; and (iii) a third high mechanical strength layer having a plurality of holes extending completely through the third high mechanical strength layer and arranged in a third pattern, the third pattern having a pore spatial arrangement that is the same as the pore spatial arrangement of the first pattern, wherein the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer can transfer through the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer. In an embodiment of this aspect, the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap less than or equal to 10% along the axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer. As used throughout this description, "same hole spatial arrangement" refers to the positions of the holes of two or more high mechanical strength layers so that they are aligned along the axis extending vertically between the high mechanical strength layers. In an embodiment, for example, "same hole spatial arrangement" refers to the positions of the holes of two or more high mechanical strength layers so that they overlap by a factor of 90% or greater along the axis extending vertically between the high mechanical strength layers.

[0013] In an embodiment, the present invention provides a separator system for an electrochemical system, comprising: (i) a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; (ii) a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern; the second pattern having an offset alignment relative to the first pattern, such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap by less than or equal to 20% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer; (iii) a third high mechanical strength layer having a plurality of holes extending completely through the third high mechanical strength layer and arranged in a third pattern; The invention further comprises a plurality of holes disposed in a third pattern having the same pore spatial arrangement as the first pattern, and (iv) a fourth high mechanical strength layer having a plurality of holes extending completely through the fourth high mechanical strength layer and disposed in a fourth pattern having the same pore spatial arrangement as the second pattern; wherein the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer can be transferred through the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer. In an embodiment of this aspect, the overlap of the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer is less than or equal to 10%.

[0014] In an embodiment, the present invention provides a separator system for an electrochemical system, comprising: (i) a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; (ii) a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern, the second pattern having an offset alignment relative to the first pattern, such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap by less than or equal to 40% along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer; and (iii) a third high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern. A plurality of holes extending through the third high mechanical strength layer and arranged in a third pattern; the third pattern has an offset alignment relative to the first pattern and the second pattern, so that the holes of the first high mechanical strength layer, the holes of the second high mechanical strength layer, and the holes of the third high mechanical strength layer overlap less than or equal to 20% along an axis extending vertically from the first layer or the second layer to the third layer; wherein the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer can be transferred through the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer. In an embodiment of this aspect, the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap less than or equal to 20% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer, and the holes of the first high mechanical strength layer, the holes of the second high mechanical strength layer, and the holes of the third high mechanical strength layer overlap less than or equal to 10% along an axis extending vertically from the first high mechanical strength layer or the second high mechanical strength layer to the third high mechanical strength layer.

[0015] In an embodiment, the present invention provides a separator system for an electrochemical system, comprising: (i) a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; (ii) a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern, the second pattern having an offset alignment relative to the first pattern, such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap less than or equal to 50% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer; (iii) a third high mechanical strength layer having a plurality of holes extending completely through the third high mechanical strength layer and arranged in a third pattern, the third pattern having an offset alignment relative to the first pattern and the second pattern, such that the holes of the first high mechanical strength layer, the holes of the second high mechanical strength layer, and the holes of the third high mechanical strength layer overlap along an axis extending vertically from the first high mechanical strength layer or the second high mechanical strength layer. (iv) a fourth high mechanical strength layer having a plurality of holes extending completely through the fourth high mechanical strength layer and arranged in a fourth pattern, the fourth pattern having an offset alignment relative to the first pattern, the second pattern, and the third pattern, such that the holes of the first high mechanical strength layer, the holes of the second high mechanical strength layer, the holes of the third high mechanical strength layer, and the holes of the fourth high mechanical strength layer overlap less than or equal to 20% along an axis extending perpendicularly from the first high mechanical strength layer or the second high mechanical strength layer to the fourth high mechanical strength layer; wherein the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer can transfer through the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer. In an embodiment of this aspect, the overlap of the holes in the first high mechanical strength layer and the holes in the second high mechanical strength layer along the axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer is less than or equal to 30%, and the offset alignment relative to the first pattern and the second pattern makes the overlap of the holes in the first high mechanical strength layer, the holes in the second high mechanical strength layer, and the holes in the third high mechanical strength layer along the axis extending vertically from the first layer or the second layer to the third layer is less than or equal to 20%, and the offset alignment relative to the first pattern, the second pattern, and the third pattern makes the overlap of the holes in the first high mechanical strength layer, the holes in the second high mechanical strength layer, the holes in the third high mechanical strength layer, and the fourth high mechanical strength layer along the axis extending vertically from the first high mechanical strength layer or the second high mechanical strength layer to the third layer is less than or equal to 10%.

[0016] In some embodiments, for example, the second high mechanical strength layer is disposed between the first high mechanical strength layer and the third high mechanical strength layer. In some embodiments, for example, the first high mechanical strength layer is disposed between the second high mechanical strength layer and the fourth high mechanical strength layer, or wherein the third high mechanical strength layer is disposed between the second high mechanical strength layer and the fourth high mechanical strength layer. In an embodiment, the first mechanical strength layer and the second mechanical strength layer are not disposed in physical contact, or the first mechanical strength layer, the second mechanical strength layer, and the third mechanical strength layer are not disposed in physical contact, or the first mechanical strength layer, the second mechanical strength layer, the third mechanical strength layer, and the fourth mechanical strength layer are not disposed in physical contact.

[0017] Some separators of this aspect, for example, provide a multilayer structure for managing dendrite formation in an electrochemical system, wherein the multilayer separator layers (e.g., first, second, third, fourth high mechanical strength layers, etc.) have complementary patterns of pores, such as microchannels or nanochannels, which establish ionic conductivity between the positive electrode and the negative electrode in a manner that dendrite growth between the positive electrode and the negative electrode is kinetically and / or thermodynamically unfavorable. Some separators of this aspect, for example, provide a barrier with a multilayer geometry and physical properties of a direct linear path to prevent dendrite growth between the positive electrode and the negative electrode, such as by providing a multilayer structure, wherein the only path for ion transfer between the positive electrode and the negative electrode requires a tortuous trajectory that is kinetically and / or thermodynamically unfavorable to dendrite growth. Without being bound by any theory, the force from the high strength layer on the dendrite slows down or stops the growth of the dendrite. In an electrochemical cell embodiment, this significantly improves the performance of the cell. In an embodiment, the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer and / or the fourth high mechanical strength layer are planar and arranged in substantially parallel directions relative to each other, for example, wherein the planar surfaces of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer and / or the fourth high mechanical strength layer are arranged in parallel planes. In an embodiment, the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer and / or the fourth high mechanical strength layer are hollow cylindrical structures and are arranged in substantially concentric directions, for example, wherein the curved surfaces of the cylindrical first layer and the second layer are arranged in concentric directions. As used herein, an axis extending perpendicularly from a concentric direction is perpendicular to a central axis and extends radially from the central axis.

[0018] The multilayer geometries of some separator systems of the present invention provide offset alignment, which provides a selected overlap of the holes of the first pattern and the holes of the second pattern along an axis extending perpendicularly from the first layer to the second layer. This aspect of the present invention is useful for obtaining useful ion transfer properties while preventing dendrite formation between the positive electrode and the negative electrode of the electrochemical cell. In some embodiments, the term "offset" refers to a configuration in which the holes of one high mechanical strength layer of the separator are offset relative to the position of the holes of another high mechanical strength layer along an axis extending from one layer to another layer, such as an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer. In some embodiments, the term "offset" refers to the relative configuration of the patterns of holes in the high mechanical strength layers, such as where the holes of the first pattern of the first high mechanical strength layer are offset relative to the position of the holes of the second pattern of the second high mechanical strength layer, so that the holes of the first high mechanical strength layer do not completely overlap the holes of the second high mechanical strength layer along the axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer. In an embodiment, for example, the first high mechanical strength layer and the second high mechanical strength layer are nano- and / or microporous and aligned so that the pores of the first high mechanical strength layer do not overlap the pores of the second high mechanical strength layer at all along the axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer. In an embodiment, for example, the overlap of the pores of two or more of the first pattern, the second pattern, the third pattern, and the fourth pattern along the axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer is less than or equal to 10%, and optionally for some applications is less than or equal to 1%. In an embodiment, for example, the overlap of the pores of two or more of the first pattern, the second pattern, the third pattern, and the fourth pattern along the axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer is selected from the range of 0 to 5%, and optionally for some applications is selected from the range of 0 to 1%. In an embodiment, for example, the overlap of the pores of two or more of the first pattern, the second pattern, the third pattern, and the fourth pattern along the axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer is equal to 0, for example, equal to 0 with good precision. In an embodiment, the overlap of the holes, for example, the first pattern, the second pattern, and the third pattern, along the axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer is less than or equal to 10%. In an embodiment, the overlap of the holes, for example, the first pattern, the second pattern, and the third pattern, along the axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer is selected from the range of 0 to 5%. In an embodiment, the overlap of the holes, for example, the first pattern, the second pattern, the third pattern, and the fourth pattern, along the axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer is less than or equal to 10%. In an embodiment, the overlap of the holes, for example, the first pattern, the second pattern, the third pattern, and the fourth pattern, along the axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer is selected from the range of 0 to 5%.

[0019] In an embodiment, for example, two or more of the first pattern, the second pattern, the third pattern, and the fourth pattern include substantially complementary patterns. In an embodiment, for example, the substantially complementary patterns correspond to substantially negative images of each other. As used herein, complementary patterns refer to a configuration in which the relative positions of the holes of a pattern of high mechanical strength layers and the holes of one or more other patterns or one or more other high mechanical strength layers are selected to prevent dendrite growth between the positive electrode and the negative electrode of the electrochemical cell. In an embodiment, for example, substantially complementary patterns of the first pattern and the second pattern are negative images of each other, for example, wherein the position of the holes of the first pattern corresponds to an area of ​​the second layer without holes. As an example of a complementary pattern of the present invention, the first layer may be characterized by a pattern of holes corresponding to the black squares of a chessboard, and the second layer may be characterized by a pattern of holes corresponding to the red squares of a chessboard. As an example of complementary patterns of the present invention, a first high mechanical strength layer may have a first periodic pattern of holes characterized by a first pitch and hole spacing, wherein a second high mechanical strength layer may have a second periodic pattern of holes characterized by the same pitch and hole spacing but offset or translated from the positions of the holes of the first pattern, such that the holes of the first high mechanical strength layer do not superimpose on the holes of the second high mechanical strength layer along an axis extending perpendicularly from the first high mechanical strength layer and the second high mechanical strength layer.

[0020] In an embodiment, a separator system having three or more high mechanical strength layers may include some high mechanical strength layers having the same pattern (i.e., non-complementary patterns), as long as at least one layer having a complementary pattern is located between high mechanical strength layers having the same pattern. For example, a separator system may feature one or more high mechanical strength layers having pattern A and one or more high mechanical strength layers having pattern B, where A and B are complementary patterns arranged according to a repeating sequence of ABA, and longer sequences are possible for multilayer systems containing four or more high mechanical strength layers, such as ABABAB.

[0021] In another embodiment, a separator system having three or more high mechanical strength layers may include only high mechanical strength layers having complementary patterns. For example, a separator system may feature one or more high mechanical strength layers having pattern A, one or more high mechanical strength layers having pattern B, and one or more high mechanical strength layers having pattern C, wherein A, B, and C are each complementary to the other two patterns, arranged according to a repeating sequence of ABC, and longer sequences (e.g., ABCABC) and varying sequences (e.g., ABCBA, ABCA) are possible for a multilayer system comprising four or more high mechanical strength layers.

[0022] In another aspect, the present invention provides a separator system further comprising one or more low ionic resistance layers disposed on the side of at least one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer. In an embodiment, for example, each of the one or more low ionic resistance layers is an electrolyte-containing layer of a reservoir providing, for example, an electrolyte of an electrochemical cell. In an embodiment, for example, each of the one or more low ionic resistance layers independently has a resistance of less than or equal to 20 ohm-cm 2 ionic resistance, and preferably for some embodiments less than or equal to 2 ohm-cm 2 , and preferably for some embodiments less than or equal to 1 ohm-cm 2 In an embodiment, for example, at least one of the one or more low ionic resistance layers is a pressure buffer layer providing space for an electrolyte disposed between at least two of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer.

[0023] In an embodiment, for example, at least one of the high mechanical strength layer and the one or more low ionic resistance layers is a deposited layer deposited on at least one of the high mechanical strength layer and the one or more low ionic resistance layers. In an embodiment, for example, at least one of the high mechanical strength layer and the one or more low ionic resistance layers is a deposited layer deposited on an electrode of an electrochemical cell, such as a layer directly deposited on the surface of a positive or negative electrode presented to the electrolyte of the electrochemical cell. In an embodiment, for example, at least one of the one or more low ionic resistance layers and optionally all low ionic resistance layers is attached to at least one side of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer by pressure, heat, or chemical attachment. In an embodiment, for example, at least one of the one or more low ionic resistance layers and optionally all low ionic resistance layers is attached to at least one side of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer by a resin polymer. In an embodiment, for example, at least one of the one or more low ionic resistance layers and optionally all low ionic resistance layers comprises a microporous material, a textile material, or a non-woven material.

[0024] In an embodiment, for example, at least one of the one or more low ionic resistance layers and optionally all low ionic resistance layers comprises a ceramic or glass electrolyte, a polymer electrolyte or another solid electrolyte. In an embodiment, for example, the low ionic resistance layer comprises a glass electrolyte, such as Nafion or ZrO2 or NASICON or LISICON or LIPON or a polymer electrolyte such as PEO. In an embodiment, for example, at least one of the one or more low ionic resistance layers and optionally all low ionic resistance layers comprises a perforated ceramic separator, a porous ceramic separator, a perforated glass separator, a porous glass separator or a perforated metal or perforated alloy separator or a perforated rubber or rubber mesh or a metal mesh or an alloy mesh.

[0025] In an embodiment, for example, at least one of the one or more low ionic resistance layers comprises a ring or frame having a central hole, such as a ring or frame structure providing a mechanical support structure, electrolyte reservoir structure and / or separator structure in an electrochemical cell. In an embodiment, for example, one or more low ionic resistance layers comprise one or more frame layers in contact with at least one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer. In an embodiment, for example, the first high mechanical strength layer is disposed between the first frame layer and the second frame layer and wherein the second high mechanical strength layer is disposed between the third frame layer and the fourth frame layer, or the first high mechanical strength layer is disposed between the first frame layer and the second frame layer and wherein the second high mechanical strength layer is disposed between the second frame layer and the third frame layer. In an embodiment, for example, one or more low ionic resistance layers comprise one or more frame layers in physical contact with at least one electrode of an electrochemical system, such as a positive electrode and / or a negative electrode of an electrochemical cell. In an embodiment, for example, one or more low ionic resistance layers include a separator disposed between the first layer and the second layer, the separator separating the first layer and the second layer by a selected distance selected from the range of 10 nm to 1000 μm and optionally for some applications selected from the range of 1 μm to 1000 μm. In an embodiment, for example, the separator of this aspect includes: a ring for establishing a selected distance between the first high mechanical strength layer and the second high mechanical strength layer; a frame structure having a porous wall component, an arrangement of material layers or discrete material elements.

[0026] In an embodiment, for example, each of the low ionic resistance layers and optionally all low ionic resistance layers is independently a polymer, ceramic, wood, glass, mineral, metal, alloy, textile material, non-woven material, cellulose, wood fiber, sponge or a combination thereof. In an embodiment, for example, one or more low ionic resistance layers each independently have a porosity greater than or equal to 50%, and preferably greater than 70% for some applications, and preferably greater than 90% for some applications. In an embodiment, for example, one or more low ionic resistance layers each independently have a porosity selected from the range of 50% to 95%, preferably a porosity selected from the range of 70% to 95% for some applications.

[0027] In an embodiment, for example, at least one side of one of the high mechanical strength layers is wettable, for example, wettable with an electrolyte of an electrochemical cell. In an embodiment, for example, a separator configuration is characterized by a wettable side of a high mechanical strength layer placed adjacent to another high mechanical strength layer, with no low ionic resistance layer disposed therebetween. In an embodiment, for example, a separator configuration is characterized by a wettable side of a high mechanical strength layer placed adjacent to an electrode, with no low ionic resistance layer disposed therebetween. In an embodiment, for example, a separator comprises one or more low ionic resistance layers or high mechanical strength layers coated on another low ionic resistance layer or high mechanical strength layer or coated on an electrode in a chemical cell, for example, a positive electrode or a negative electrode of an electrochemical system.

[0028] In another aspect, the present invention provides a separator, which also includes one or more chemical barrier layers disposed on the side of at least one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, or one or more low ionic resistance layers. A separator with one or more chemical barriers is useful in an electrochemical system, wherein the positive electrode and the negative electrode are arranged to contact different electrolytes, and thus the chemical barrier allows the transfer of charge carriers, but prevents the transfer of electrolytes. In such a configuration, the chemical barrier is useful for protecting the electrode from degradation and / or enabling the use of different electrolytes for the positive and negative electrodes of the electrochemical cell. In an embodiment, for example, one or more chemical barrier layers independently prevent unwanted chemical components from being transferred to the positive or negative electrode of the electrochemical cell through one or more chemical barrier layers. In an embodiment, for example, one or more chemical barrier layers prevent electrolyte solvents from being transferred to the positive or negative electrode of the electrochemical cell through one or more chemical barrier layers. In an embodiment, for example, one or more chemical barrier layers include a solid electrolyte or a solid polymer electrolyte disposed on at least one side of an electrode of an electrochemical cell. In an embodiment, for example, one or more chemical barrier layers include a solid electrolyte from LISICON or NASICON or a polymer electrolyte including polyethylene oxide (PEO).

[0029] In an embodiment, for example, the separator system is a component of an electrochemical cell having a negative electrode and a positive electrode, wherein one or more chemical barrier layers include an ion-conducting protective membrane, wherein the protective membrane provides a barrier between a first electrolyte in contact with the positive electrode and a second electrolyte in contact with the negative electrode, wherein the ion-conducting protective membrane prevents contact between the negative electrode and the first electrolyte. In an embodiment, for example, the negative electrode is a lithium metal electrode, wherein the ion-conducting protective membrane conducts lithium ion charge carriers and prevents contact between the lithium metal electrode and the first electrolyte.

[0030] In an embodiment, for example, the ion-conducting protective membrane comprises a material selected from the group consisting of a glassy or amorphous active metal ion conductor, a ceramic active metal ion conductor, and a glass-ceramic active metal ion conductor. In an embodiment, for example, one or more chemical barrier layers also include a solid polymer electrolyte arranged between the surface of the protective membrane and the positive electrode or the negative electrode. In an embodiment, for example, at least one of the high mechanical strength layer, one or more low ionic resistance layers, and one or more chemical barrier layers is a deposition layer deposited on at least one of the high mechanical strength layer, one or more low ionic resistance layers, and one or more chemical barrier layers. In an embodiment, for example, at least one of the high mechanical strength layer, one or more low ionic resistance layers, and one or more chemical barrier layers is a deposition layer deposited on an electrode of an electrochemical cell. In an embodiment, for example, the separator comprises a combination of at least two of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer and one or more chemical barrier layers, without any low ionic resistance layer.

[0031] In one aspect, the separator further comprises a third high mechanical strength layer having a plurality of holes extending completely through the third high mechanical strength layer and arranged in a third pattern; the third high mechanical strength layer is located between the first high mechanical strength layer and the second high mechanical strength layer; the third pattern has an offset alignment relative to the first pattern or the second pattern, such that the holes of the first pattern or the second pattern and the holes of the third pattern overlap less than or equal to 20% along an axis extending perpendicularly from the first high mechanical strength layer or the second high mechanical strength layer to the third high mechanical strength layer. In one aspect, the separator further comprises a fourth high mechanical strength layer having a plurality of holes extending completely through the fourth high mechanical strength layer and arranged in a fourth pattern; the fourth high mechanical strength layer is located between the first high mechanical strength layer and the second high mechanical strength layer, the fourth pattern has an offset alignment relative to the first pattern, the second pattern, or the third pattern, such that the holes of the first pattern, the second pattern, or the third pattern and the holes of the fourth pattern overlap less than or equal to 20% along an axis extending perpendicularly from the first high mechanical strength layer or the second high mechanical strength layer to the fourth high mechanical strength layer.

[0032] The layers of the multilayer separator system of the present invention can be configured and connected via various mechanisms and equipment arrangements to provide mechanical properties useful for specific applications. In an embodiment, for example, at least a portion of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the low ionic resistance layer, the frame layer, the separator, the chemical barrier layer, and optionally all or any combination of these are at least partially connected to each other by pressure, heating, adhesive coating, chemical attachment, plasma treatment, or any combination of these. In an embodiment, for example, at least a portion of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the low ionic resistance layer, the frame layer, the separator, the chemical barrier layer, and optionally all or any combination of these are at least partially connected to each other via glue, epoxy resin, adhesive, PTFE, solid electrolyte, gel electrolyte, polymer electrolyte, silicone adhesive, acrylic adhesive, cyanoacrylate, stycast 1266, deltabond 151, PVDF, PVA, LIPON, LISICON, PE-PP-PVDF, tetramethylammonium hydroxide pentahydrate (CH3)4NOH·5H2O, poly(ethylene oxide) (PEO), copolymer of epichlorohydrin and ethylene oxide P(ECH-co-EO) and poly(vinyl alcohol), glass fiber polymer electrolyte, zinc sulfide, silica, Kapton tape, polyethylene oxide or polypropylene oxide or copolymer PVDF-co-HFP Bi2O3, fluorine-free adhesive or aromatic adhesive, lithium polyacrylate or a combination thereof.

[0033] In an embodiment, the present invention provides a separator system further comprising one or more solid electrolyte layers that prevent, for example, water molecules, CO2, O2, or air from transferring through the separator system, wherein the one or more solid electrolyte layers comprise LISICON or NASICON.

[0034] In one aspect, the separator of the present invention further comprises one or more electrolytes, such as an electrolyte of an electrochemical cell, which is optionally in physical contact with at least a portion of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the low ionic resistance layer, the frame layer, the separator, the chemical barrier layer, or any combination thereof. In an embodiment, for example, the separator system is a component of an electrochemical cell having a positive electrode and a negative electrode, and the separator further comprises an electrolyte disposed between the positive electrode and the negative electrode; wherein the electrolyte is in contact with any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer. In an embodiment, for example, the separator system is a component of an electrochemical cell having a positive electrode and a negative electrode, the separator further comprising a first electrolyte and a second electrolyte disposed between the positive electrode and the negative electrode; wherein the first electrolyte has a different composition than the second electrolyte; wherein the first electrolyte is in contact with any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and wherein the second electrolyte is in contact with any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, wherein the first electrolyte and the second electrolyte do not mix with each other due to the presence of an impermeable ion-conducting layer between them or due to different chemical and physical properties, such as hydrophilic or hydrophobic behavior or density.

[0035] The physical, chemical, and electronic properties of the components of the separator system, such as the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, are selected to provide net separator properties useful for applications in electrochemical cells, such as providing a combination of high electrical resistance, high ionic conductivity, and useful mechanical properties.

[0036] In an embodiment, for example, the first pattern of holes provides a first porosity of the first high mechanical strength layer greater than or equal to 30% and preferably greater than 40% for some applications, and / or wherein the second pattern of holes provides a second porosity of the second high mechanical strength layer greater than or equal to 30% and preferably greater than 40% for some applications. In an embodiment, for example, the first pattern of holes provides a first porosity of the first high mechanical strength layer greater than or equal to 30% and preferably greater than 40% for some applications, or wherein the second pattern of holes provides a second porosity of the second high mechanical strength layer greater than or equal to 30% and preferably greater than 40% for some applications; or wherein the third pattern of holes provides a third porosity of the third high mechanical strength layer greater than or equal to 30% and preferably greater than 40% for some applications; or wherein the fourth pattern of holes provides a fourth porosity of the fourth high mechanical strength layer greater than or equal to 30% and preferably greater than 40% for some applications. In an embodiment, for example, the first pattern of holes provides a porosity of the first high mechanical strength layer selected from the range of 30% to 70%, and preferably for some applications 40% to 70%; and wherein the second pattern of holes provides a porosity of the second high mechanical strength layer selected from the range of 30% to 70%, and preferably for some applications 40% to 70%. In an embodiment, for example, the first pattern of holes provides a porosity of the first high mechanical strength layer selected from the range of 30% to 70%, and preferably for some applications 40% to 70%; or wherein the second pattern of holes provides a porosity of the second high mechanical strength layer selected from the range of 30% to 70%, and preferably for some applications 40% to 70%; or wherein the third pattern of holes provides a porosity of the third high mechanical strength layer selected from the range of 30% to 70%, and preferably for some applications 40% to 70%; or wherein the fourth pattern of holes provides a porosity of the fourth high mechanical strength layer selected from the range of 30% to 70%, and preferably for some applications 40% to 70%.

[0037] Various geometries, shapes, directions and patterns of the holes of the high mechanical strength layer are useful in the separator system of the present invention. In an embodiment, for example, the holes of any of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer or the fourth high mechanical strength layer independently have a cross-sectional shape selected from the group consisting of a circle, a parallelogram, a rectangle, a square, a triangle, an ellipse, a quadrilateral, a pentagon, a hexagon and any combination thereof. In an embodiment, for example, the holes of the high mechanical strength layer have at least one lateral dimension (e.g., length, width, diameter, etc.) greater than or equal to 20 μm, optionally greater than or equal to 50 μm for some embodiments, optionally greater than or equal to 200 μm for some embodiments, optionally greater than or equal to 500 μm for some embodiments. In an embodiment, for example, the holes of the high mechanical strength layer have at least one lateral dimension between 1 μm and 1 mm and optionally between 200 μm and 1 mm for some applications. In an embodiment, for example, the pores of the high mechanical strength layer have at least one lateral dimension less than or equal to 200 μm, and optionally for some applications less than or equal to 10 μm, and optionally for some applications less than or equal to 1 μm. In an embodiment, for example, any of the first pattern, the second pattern, the third pattern, or the fourth pattern is independently a symmetrical pattern of pores or an asymmetrical pattern of pores. In an embodiment, for example, any of the first pattern, the second pattern, the third pattern, or the fourth pattern independently comprises a pattern of pores that is not random.

[0038] In an embodiment, for example, any of the first pattern of holes, the second pattern of holes, the third pattern of holes, or the fourth pattern of holes is independently manufactured by a process selected from the group consisting of laser cutting, lithography, etching, casting, drilling, molding, stamping, patterning, coating, and any combination of these.

[0039] In an embodiment, the first high mechanical strength layer, and / or the second high mechanical strength layer, and / or the third high mechanical strength layer, and / or the fourth high mechanical strength layer are non-conductive, for example, one or more of these layers include an electrically insulating material to prevent direct electrical contact between the positive electrode and the negative electrode of an electrochemical system such as an electrochemical cell. The electrically insulating high mechanical strength layer may include various electrically insulating materials such as Kapton, polyester, Al2O3, polyethylene, polypropylene, fibrous cellulose and / or a metal layer coated with an electrical insulator such as PE and PP coating. In an embodiment, at least one of the first high mechanical strength layer, and / or the second high mechanical strength layer, and / or the third high mechanical strength layer, and / or the fourth high mechanical strength layer is conductive, for example, wherein one or more of these layers include an electrically insulating material and one or more of these layers include a conductive material. The first high mechanical strength layer, and / or the second high mechanical strength layer, and / or the third high mechanical strength layer, and / or the fourth high mechanical strength layer include a material characterized by shape memory properties such as a shape memory polymer or a material characterized by superelastic properties.

[0040] In an embodiment, for example, the first high mechanical strength layer and the second high mechanical strength layer are not completely in physical contact with each other, for example, they are arranged in a configuration where there is at least some space between the first high mechanical strength layer and the second high mechanical strength layer to allow electrolyte ion transfer, for example, provided by the first high mechanical strength layer and the second high mechanical strength layer having rough surfaces in contact with each other, so that at some points they are physically connected, but at some other points there is some space between them. In an embodiment, the first high mechanical strength layer and the second high mechanical strength layer are not in physical contact or are not completely in physical contact. In an embodiment, for example, at least a portion of the first high mechanical strength layer and the second high mechanical strength layer are separated by a distance selected from the range of 20 nm to 2 mm. In an embodiment, for example, at least a portion of the first high mechanical strength layer or the second high mechanical strength layer is separated from the third high mechanical strength layer or the fourth high mechanical strength layer by a distance selected from the range of 20 nm to 2 mm.

[0041] In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, one or more low ionic resistance layers, and one or more chemical barrier layers, and optionally all independently have an average thickness selected in the range of 10 nm to 1 mm, and optionally for some applications in the range of 1 μm to 500 μm, and optionally for some applications in the range of 10 nm to 50 μm. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, one or more low ionic resistance layers, and one or more chemical barrier layers, and optionally all independently have an average thickness selected in the range of 5 μm to 1 mm, and optionally for some applications in the range of 25 μm to 5 mm, and optionally for some applications in the range of 100 μm to 2 mm, and optionally for some applications in the range of 500 μm to 1 mm. In an embodiment, for example, any one and optionally all of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the one or more low ionic resistance layers, and the one or more chemical barrier layers independently have an average thickness selected in the range of 10 nm to 2 μm or in the range of 2 μm to 50 μm.

[0042] In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently have a Young's modulus selected in the range of 500 MPa to 500 GPa. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently have a yield strength selected in the range of 5 MPa to 1000 MPa. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently have a propagating tear strength selected in the range of 0.005 N to 10 N, preferably a propagating tear strength greater than 0.01 N for some applications. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently have an initiating tear strength selected in the range of 10 N to 500 N, preferably an initiating tear strength greater than 50 N for some applications. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently have a tensile strength selected in the range of 50 MPa to 2 GPa. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently have an impact strength selected in the range of 10 N cm to 1000 N cm.

[0043] In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include a planar layer arranged in a parallel configuration. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include a hollow cylindrical layer arranged in a concentric configuration. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, one or more low ionic resistance layers, and one or more chemical barrier layers, and optionally all independently include a chemically resistant material. In an embodiment, for example, the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, one or more low ionic resistance layers, and one or more chemical barrier layers are independently chemically compatible with an electrolyte arranged in contact with it and / or independently chemically compatible with an electrode arranged in contact with it.

[0044] In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include a material having a melting point greater than or equal to 100 degrees Celsius. In an embodiment, for example, at least two of the high mechanical strength layers have different melting temperatures that differ by at least 30 degrees Celsius, optionally, wherein the difference in the melting temperatures of the high mechanical strength layers provides a shutdown mechanism, wherein the shutdown mechanism is that the ion path between the two electrodes of the electrochemical cell is closed by melting one of the layers; or optionally, wherein the difference in the melting temperatures of the high mechanical strength layers does not provide a shutdown mechanism, wherein the ion path between the two electrodes of the electrochemical cell is closed by melting one of the layers. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include a material having a thermal conductivity of thermal expansion less than or equal to 50 ppm / °C.

[0045] The first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer of the separator system of the present invention may include various materials selected for specific applications such as the type of electrochemical battery. In an embodiment, for example, the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer independently include chemically resistant materials. In an embodiment, for example, the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer independently include thermally stable materials. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include one or more materials selected from the group consisting of polymers, metals, alloys, ceramics, wood, glass, semiconductors, textile materials, and non-woven materials. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include a material having a dielectric constant greater than or equal to 50. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include a conductive material. In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include one or more materials selected from the group consisting of a gel electrolyte, a solid electrolyte, and a polymer electrolyte.In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer, and optionally all independently include a material selected from polyacrylic acid (PAA), cross-linked polyethylene (PEX, XLPE), polyethylene (PE), polyethylene terephthalate (PET, PETE), polyphenylene ether (PPE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polylactic acid (PLA), polypropylene (PP), polybutylene (PB), polybutylene terephthalate (PBT), polyamide (PA), polyimide (PI), polycarbonate (PC), polytetrafluoroethylene (PTFE), polystyrene ( PS), polyurethane (PU), polyester (PE), acrylonitrile-butadiene-styrene (ABS), poly(methyl methacrylate) (PMMA), polyoxymethylene (POM), polysulfone (PES), styrene-acrylonitrile (SAN), ethylene-vinyl acetate (EVA), styrene-maleic anhydride (SMA), PVDF, PEO, LIPON, LISICON, Nafion, ZrO2, NASICON, tetramethylammonium hydroxide pentahydrate (CH3)4NOH·5H2O, poly(ethylene oxide) (PEO), copolymers of epichlorohydrin and ethylene oxide P(ECH-co-EO) and poly(vinyl alcohol), PEO– PVA-glass fiber polymer electrolyte, zinc sulfide, silica, PVA and PSA, PVA / V6 / PSS; PVAN6 / (PSS+PAA); V6 / PVA / (PSS+PAA); PVM PSS+PAA(35%)) / (PSS+PAA(35%)); (PSS+PAA(35%)) / PVA / (PSS+PAA(35%)); or (PSS+PAA(35%)) / (PVA(10%)+PSS(20% relative to PVA)) / (PSS+PAA (35%)), polyethylene glycol, polypropylene glycol, polybutylene glycol, alkyl-polyethylene glycol, alkyl-polypropylene glycol, alkyl-polybutylene glycol, copolymers thereof, PEO materials or PVA materials and one or more materials of the group consisting of any combination thereof.

[0046] In an embodiment, for example, the surface of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer can be wetted with an electrolyte. In an embodiment, for example, the surface of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer is coated with a coating that can be wetted with an electrolyte. In an embodiment, for example, at least a portion of the surface of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer is coated with an adhesive coating, optionally covering at least 10% of the surface. In an embodiment, for example, at least a portion of the surface of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer is coated with an adhesive coating having a thickness of less than 5 μm. In an embodiment, for example, at least one surface of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer has a surface roughness, such as a surface roughness characterized by an rms (root mean square) selected from the range of 1 nm to 1000 nm, which provides space for an electrolyte between at least a portion of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, or the fourth high mechanical strength layer. In an embodiment, for example, the separator system is a component in an electrochemical cell having a positive electrode and a negative electrode; wherein at least one surface of any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer has a surface roughness, such as a surface roughness characterized by an rms selected from the range of 1 nm to 1000 nm, which provides space for an electrolyte between the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, or the fourth high mechanical strength layer and the positive electrode or negative electrode of the electrochemical cell. In an embodiment, for example, the surface roughness provides a distance selected from the range of 5 nm and 5 microns between at least a portion of two of the high mechanical strength layers or between the high mechanical strength layer and at least a portion of the positive electrode or the negative electrode.

[0047] In one aspect, the present invention provides a separator system wherein at least some of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the low ionic resistance layer, the frame layer, the separator, the chemical barrier layer, or any combination thereof have a high surface energy, preferably greater than or equal to 10 mJ / m for some applications. 2 In an embodiment, for example, the surface energy of any of these components facilitates wettability of the layer to the electrolyte. In an embodiment, for example, the surface energy of any of these components helps the layers connect to each other or to the electrodes of the electrochemical cell.

[0048] In one aspect, the separator further comprises one or more coatings disposed on any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer. In an embodiment, for example, one or more coatings independently comprise one or more non-conductive coatings. In an embodiment, for example, one or more coatings independently comprise one or more hydrophobic coatings and / or hydrophilic coatings. In an embodiment, for example, one or more coatings independently comprise polyethylene glycol. In an embodiment, for example, one or more coatings prevent material from being transferred from the positive electrode to the negative electrode of the electrochemical cell. In an embodiment, for example, one or more coatings independently have a thickness selected from a range of 10 nm to 2 μm. In an embodiment, for example, the separator is used for an electrochemical cell having a sulfur-based cathode, wherein one or more coatings repel hydrophobic polysulfides and increase the performance and cycle life of the electrochemical cell. In an embodiment, a hydrophilic or hydrophobic coating is provided for a sulfur-based cathode Li battery. The problem with the prior art of sulfur-based cathode Li batteries is that the electrochemical reaction can be dissolved in the electrolyte, and therefore there may be a significant capacity loss caused by the transfer of materials (intermediate polysulfides) from the sulfur electrode through the electrolyte to the Li electrode. To prevent this problem, separators of certain embodiments are coated with a polyethylene glycol material (hydrophilic), which repels hydrophobic polysulfides and thus impedes material passage and capacity loss. The use of coatings in embodiments of the invention is also useful in protecting the Li anode from moisture, such as by hydrophobic coatings on separators in lithium-air and lithium-water electrochemical cells, for example.

[0049] In an embodiment, for example, any one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer is independently a metal layer optionally selected from the group consisting of Al, Ni, Cu, and stainless steel. In an embodiment, for example, the coating is a non-conductive coating optionally including PTFE, PE, PP, PVC, or polyimide.

[0050] The present invention includes separator systems useful for various electrochemical systems. In an embodiment, for example, the present invention provides a separator system for a primary electrochemical cell or a secondary electrochemical cell. In an embodiment, for example, the present invention provides a separator system for a lithium battery, an alkaline battery, a zinc battery, or a lead-acid battery. In an embodiment, for example, the present invention provides a separator system for a lithium metal-air battery, a lithium ion battery, a lithium-air battery, a Fe-air battery, an Al-air battery, or a zinc-air battery. In an embodiment, for example, the present invention provides a separator system for a fuel cell, a flow battery system, a semi-solid battery, a 3D battery, a nanobattery, a microbattery, or an electrolyte capacitor.

[0051] In another aspect, the present invention provides an electrochemical cell comprising: (i) a negative electrode; (ii) a positive electrode; (iii) a first electrolyte disposed between the positive electrode and the negative electrode; and (iv) a separator system of the present invention disposed in contact with the electrolyte and between the negative electrode and the positive electrode; wherein the separator system is positioned so that ions of the electrolyte can be transferred between the positive electrode and the negative electrode. In one aspect, the separator system prevents electrical contact between the positive electrode and the negative electrode. As will be appreciated by those skilled in the art, any separator system described herein can be used in the electrochemical systems of the present invention, such as electrochemical cells.

[0052] In an embodiment, for example, the separator system is disposed in physical contact with the positive electrode and the negative electrode. In an embodiment, for example, the separator system provides equal to or greater than 1x10 -3 S / cm, optionally preferably greater than 1x10 for some applications -2 S / cm between the positive electrode and the negative electrode. In an embodiment, for example, the separator system provides an ionic conductivity of 0.5 ohm cm 2 to 25 ohm cm 2 range and preferably less than 5 ohm cm for some applications 2 The net ionic resistance from the positive electrode to the negative electrode.

[0053] In an embodiment, the electrochemical cell further comprises a chemical barrier layer disposed between the positive electrode and the negative electrode; the electrochemical cell further comprises a second electrolyte disposed between the positive electrode and the negative electrode, wherein the chemical barrier layer prevents mixing of the first electrolyte and the second electrolyte.

[0054] In an embodiment, for example, the offset alignment of the high mechanical strength layer does not provide a direct linear path between the positive electrode and the negative electrode. In an embodiment, for example, the offset alignment prevents short circuiting of the electrical contact between the positive electrode and the negative electrode by manufacturing defects, foreign objects, or the formation of dendrites on the positive electrode or the negative electrode. Embodiments of this aspect are, for example, useful for minimizing or preventing electrical short circuits or thermal runaway problems from the positive electrode to the negative electrode caused by the formation of dendrites. Embodiments of this aspect are, for example, useful for providing an electrochemical cell capable of enhancing cycling and / or high discharge rate performance.

[0055] In an embodiment, for example, at least one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the low ionic resistance layer, the frame layer, the separator, the chemical barrier layer, or any combination thereof is at least partially connected to the positive electrode or the negative electrode by pressure, heating, adhesive coating, chemical attachment, plasma treatment, or by depositing or coating one layer on another layer or on the electrode, or any combination thereof. In an embodiment, for example, at least one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the low ionic resistance layer, the frame layer, the separator, the chemical barrier layer, or any combination thereof is at least partially connected to the positive electrode or the negative electrode by glue, epoxy resin, adhesive, Teflon coating, solid electrolyte, gel electrolyte, or polymer electrolyte. In an embodiment, for example, at least one of the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, the fourth high mechanical strength layer, the low ionic resistance layer, the frame layer, the separator, the chemical barrier layer, or any combination thereof comprises a coating deposited on the surface of the positive electrode or the negative electrode.

[0056] In an embodiment, for example, the present invention provides an electrochemical cell incorporating a current separator system having a cycling capacity of at least 300 cycles and preferably at least 500 cycles for some applications. In an embodiment, for example, the present invention provides an electrochemical cell incorporating a current separator system having a cycling capacity of at least 300 cycles and preferably at least 500 cycles for some applications. -1 An electrochemical cell having a specific capacity of a current separator system. In an embodiment, for example, the present invention provides an electrochemical cell.

[0057] The electrochemical cell and separator system of the present invention are compatible with various electrolytes, including liquid electrolytes, solid electrolytes, gel electrolytes, aprotic electrolytes, aqueous electrolytes, and non-aqueous electrolytes. In an embodiment, for example, the electrolyte comprises a solid charged dielectric or a gel electrode. In an embodiment, for example, the electrolyte comprises a polymeric medium. In an embodiment, for example, the electrolyte comprises polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, fluorinated copolymers, polyacrylonitrile, and any combination thereof.

[0058] In an embodiment, for example, the electrolyte includes an alkali metal salt at least partially dissolved in one or more non-aqueous solvents. In an embodiment, for example, the electrolyte includes a solvent and a supporting salt; wherein the solvent is selected from the group consisting of organic carbonates, ethers, esters, formates, lactones, sulfones, cyclopentane, 1,3-dioxolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, fluoropropylene carbonate, y-butyrolactone, methyl difluoroacetate, ethyl difluoroacetate, dimethoxyethane, diethylene glycol dimethyl ether (bis(2-methoxyethyl) ether), tetrahydrofuran, dioxolane, 2MeTHF, 1,2-DME or higher glycol dimethyl ether, cyclopentane, methyl formate, methyl acetate and any combination thereof; and wherein the supporting salt is selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiClO4, LiSO3CF3, LiN(CF3SO2)2, LiN(SO2C2F5)2 and any combination thereof. In an embodiment, for example, the electrolyte includes a golfing agent selected from the group consisting of PVdF, PVdF-HFP copolymer, PAN and PEO, and mixtures thereof; a plasticizer selected from the group consisting of EC, PC, DEC, DMC, EMC, THE, 2MeTHF, 1,2-DME, and mixtures thereof; and a Li salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiClO4, LiSO3CF3, LiN(CF3SO2)2, and LiN(SO2C2F5)2.

[0059] In one aspect, the present invention provides an electrochemical cell having a first electrolyte on a first side of the cell comprising a positive electrode and a second electrolyte on a second side of the cell comprising a negative electrode, wherein the first electrolyte has a different composition than the second electrolyte, and wherein the electrochemical cell further comprises one or more chemical barrier layers comprising an ion-conducting protective membrane positioned between the positive electrode and the negative electrode. In an embodiment of this aspect, the first electrolyte is an aqueous electrolyte and the second electrolyte is an aprotic electrolyte. In an embodiment of this aspect, at least one of the first electrolyte and the second electrolyte is a solid electrolyte.

[0060] The electrochemical cell and separator system of the present invention are compatible with electrodes having various compositions, form factors and device geometries. In an embodiment, for example, the negative electrode, the positive electrode or both include micron-sized materials or nano-sized materials. As used herein, nano-sized refers to a structure such as a particle or a film having at least one physical dimension (e.g., length, height, width, diameter, etc.) selected in the range of 1nm to 1000nm. As used herein, micron-sized refers to a structure such as a particle or a film having at least one physical dimension (e.g., length, height, width, diameter, etc.) selected in the range of 1μm to 1000μm. In an embodiment, for example, the negative electrode or the positive electrode is in the form of a powder, such as a mixture of active electrode particles and conductive particles. In an embodiment, for example, the negative electrode or the positive electrode is in the form of a film. In an embodiment, for example, the present invention provides an electrochemical cell, wherein at least one of the positive electrode or the negative electrode is in the form of a solvated metal such as solvated lithium or a solvated lithium alloy. In an embodiment, for example, the present invention provides an electrochemical cell, wherein at least one of the positive electrode or the negative electrode is in the form of a molten metal.

[0061] In an embodiment, for example, the present invention provides an electrochemical cell wherein the negative electrode comprises a transition metal sodium phosphate, a mixed metal sodium phosphate, a Li 4 / 3 Ti 5 / 3 O4, graphite, tin alloy, cobalt, carbon, LiVO2, Li4Ti5O 12 , Li 4 / 3 Ti 5 / 3 In one embodiment, for example, the present invention provides an electrochemical cell wherein the positive electrode comprises a material selected from the group consisting of graphite, LiCoO2NiO8O2, LiNiO2, LiFePO4, LiMnPO4, LiCoPO4, LiMn2O4, LiCoO2, LiNiO5Mn l.5 O4, LiVPO4F, silver oxide, nickel oxide, cobalt oxide, manganese oxide, AgO, Ag2O3, Zn, ZnO AgO, Ag2O, Ag2O3, HgO, Hg2O, CuO, CdO, NiOOH, Pb2O4, PbO2, LiFePO4, Li3V2(PO4)3, V6O 13 , V2O5, Fe3O4, Fe2O3, MnO2, LiCoO2, LiNiO2, LiMn2O4, LiVO2, Li4Ti5O 12, TiO2, WO2 and MoO2. In an embodiment, for example, the present invention provides an electrochemical cell, wherein the positive electrode comprises a material selected from the group consisting of: (i) a material selected from the group consisting of LixCoO2, Li x A lithiated metal oxide based cathode from the group consisting of NiO2, LixMn2O4 and LiFePO4; (ii) a cathode selected from Ag x V2O5、Cu x V2O5, V2O5, V6O 13 , MnO2, CuO, Ag2CrO4 and MoO3, wherein x ranges from 0 to 2; (iii) a lithiated metal oxide based cathode selected from the group consisting of FeS2, TiS2, FeS and CuS; (iv) an active sulfur cathode selected from the group consisting of elemental sulfur, polysulfides and combinations thereof; and (v) a PEO / carbon / metal oxide type cathode structure comprising an aqueous electrochemically active component such as water or a water-soluble oxidant selected from the group consisting of gaseous, liquid and solid oxidants and combinations thereof such as peroxides, hydrogen peroxide, O2, SO2 and NO2, and the water-soluble solid oxidant is selected from the group consisting of NaNO2, KNO2, Na2SO3 and K2SO3, wherein the cathode structure conductive component is a porous catalytic support such as nickel, and wherein the cathode structure electrochemically active material comprises air.

[0062] The electrochemical cell of the present invention includes a primary electrochemical cell and a secondary electrochemical cell. In an embodiment, for example, the present invention provides an electrochemical cell including a lithium battery, an alkaline battery, a zinc battery, a lead-acid battery, a lithium metal-air battery, a lithium ion battery, a lithium-air battery, a Fe-air battery, an Al-air battery or a zinc-air battery. In an embodiment, for example, the present invention provides an electrochemical cell including a fuel cell, a flow battery system, a semi-solid battery, a 3D battery, a nanobattery, a microbattery or an electrolyte capacitor. In an embodiment, for example, the present invention provides an electrochemical cell including a thin film battery. In an embodiment, for example, the present invention provides an electrochemical cell as an alkali metal ion battery.

[0063] In an embodiment, for example, the present invention provides a battery comprising one or more electrochemical cells, such as one or more lithium ion electrochemical cells. As will be appreciated by those skilled in the art, any of the separator systems and electrochemical cells described herein can be used in the alkali metal flow batteries, supercapacitors or fuel cells of the present invention.

[0064] In one aspect, the present invention provides an alkali metal fuel cell comprising: (i) a regenerative anode comprising a solid alkali metal and an alkali metal dissolved in a solvent as a fuel; (ii) a cathode structure comprising a static electronically conductive component, an ion-conducting component of an electrolyte comprising ions of the alkali metal, and a fluid oxidant obtained from the operating environment of the cell; and (iii) a separator system of the present invention disposed between the anode and cathode structures. As will be appreciated by those skilled in the art, any separator system described herein may be used in the alkali metal flow battery, supercapacitor, or fuel cell of the present invention.

[0065] In one aspect, the present invention provides a method of making an electrochemical cell, the method comprising the steps of: (i) providing a negative electrode; (ii) providing a positive electrode; (iii) providing an electrolyte between the positive electrode and the negative electrode; and (iv) providing a separator system located between the positive electrode and the negative electrode, wherein the separator system comprises (i) a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; and (ii) a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern; the second pattern having an offset alignment relative to the first pattern such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap by less than or equal to 20% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer; wherein the first high mechanical strength layer and the second high mechanical strength layer are positioned such that ions of the electrolyte disposed in contact with the first high mechanical strength layer and the second high mechanical strength layer can be transferred through the first high mechanical strength layer and the second high mechanical strength layer. In an embodiment, the separator system is in at least partial physical contact with the electrolyte. In an embodiment, the method further comprises disposing an ion-conducting chemical barrier between the positive electrode and the negative electrode; wherein the ion-conducting chemical barrier separates a first electrolyte in contact with the positive electrode and a second electrolyte in contact with the negative electrode; wherein the first electrolyte has a different composition than the second electrolyte; and wherein the ion-conducting chemical barrier prevents mixing of the first electrolyte and the second electrolyte. As will be generally understood by those skilled in the art, any of the current separator systems and the system of the present invention - including all specific embodiments and combinations of components, materials and properties described herein - can be used in the current method of making an electrochemical cell.

[0066] In one aspect, the present invention provides a method of generating an electric current, the method comprising the steps of: (i) providing an electrochemical cell, wherein the electrochemical cell comprises: (1) a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; and (2) a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern; the second pattern having an offset alignment relative to the first pattern such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap by less than or equal to 20% along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer; wherein the first high mechanical strength layer and the second high mechanical strength layer are positioned such that ions of an electrolyte disposed in contact with the first high mechanical strength layer and the second high mechanical strength layer can be transferred through the first high mechanical strength layer and the second high mechanical strength layer; and (ii) discharging the electrochemical cell. In an embodiment, the method of this aspect further comprises the step of charging the electrochemical cell. In an embodiment, the method of this aspect further comprises the step of cycling the electrochemical cell in a plurality of charge and discharge cycles. As will be generally understood by one skilled in the art, any of the present separator systems and the system of the present invention - including all specific embodiments and combinations of components, materials and characteristics described herein - can be used in the present method of generating electrical current.

[0067] In another aspect, an electrochemical cell is provided that includes: a positive electrode; a negative electrode; an ionically conductive and electronically insulating separator positioned between the positive electrode and the negative electrode; a first electronically and ionically conductive layer positioned between the positive electrode and the separator and in electrical contact with the positive electrode, or positioned between the negative electrode and the separator and in electrical contact with the negative electrode; and one or more electrolytes positioned between the positive electrode and the negative electrode; wherein the one or more electrolytes are capable of conducting charge carriers.

[0068] Optionally, the first electronically and ionically conductive layer comprises a metal, a metal alloy, a carbon material, a semiconductor, a conductive polymer, a conductive ceramic, or any combination of these. Optionally, the first electronically and ionically conductive layer comprises a metal or alloy mesh, a metal or alloy perforated layer, a metal or alloy coating, a carbon coating, a porous layer, a perforated layer, a mesh, a foam, at least a partial coating of a conductive material, or any combination of these. Optionally, the first electronic and ion conductive layer comprises any of Au, Al, Cu, Ti, Zn, Ag, stainless steel, Li, Sn, Si, Ni, steel, tungsten, tin, lead, constantan, mercury, germanium or alloys thereof, graphite, carbon black, graphene, carbon nanotubes, coke, Li alloy, Fe alloy, indium tin oxide (ITO), lanthanum-doped strontium titanate (SLT), yttrium-doped strontium titanate (SYT), polyfluorenes, polyphenylenes, polypyrenes, polyazulenes, polynaphthalenes, polyacetylenes, poly(p-phenylene vinylene), polypyrroles, polycarbazoles, polyindoles, polyazepines, polyanilines, Polythiophenes, poly(3,4-ethylenedioxythiophene), poly(p-phenylene sulfide), polyfluorene-based conductive polymers, PAN, poly(9,9-dioctylfluorene-co-fluorenone), poly(9,9-dioctylfluorene-co-fluorenone-co-methylbenzoate), polythiophene, polypyrrole, poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT:PSS), [(ferrocenyl)aminopropyl]pyrrole, pyrrole, polypyrrole, polyaniline, polythiophene, polyfuran, SiO2, Napon, PVC or doped compositions thereof or mixtures thereof; or any combination thereof.

[0069] Optionally, the first electronically and ionically conductive layer comprises a porous or perforated material having a porosity greater than or equal to 30%, greater than or equal to 40%, greater than or equal to 50%, greater than or equal to 60%, greater than or equal to 70%, greater than or equal to 80%, greater than or equal to 90%, selected from the range of 30% to 90%, selected from the range of 40% to 80%, selected from the range of 50% to 70%, or selected from the range of 50% to 90%.

[0070] Optionally, the first electronic and ion conductive layer comprises a chemically resistant material, a heat resistant material, a hard material, or any combination of these materials. Optionally, the first electronic and ion conductive layer comprises a thin film structure deposited on at least one outer surface of the separator, the positive electrode, or the negative electrode. Optionally, the first electronic and ion conductive layer comprises a coating applied to at least one outer surface of the separator, the positive electrode, or the negative electrode.

[0071] Optionally, the first electronically and ionically conductive layer comprises a porous, perforated or foamed material having a porosity greater than or equal to 30%.

[0072] Optionally, at least a portion of the first electronic and ion conductive layer is located within the active material of the positive electrode or within the active material of the negative electrode. Optionally, the portion of the first electronic and ion conductive layer located within the active material of the positive electrode or within the active material of the negative electrode is not in physical contact with the separator. Optionally, the portion of the first electronic and ion conductive layer located within the active material of the positive electrode or within the active material of the negative electrode is in physical contact with the current collector of the positive electrode or the current collector of the negative electrode. Optionally, the portion of the first electronic and ion conductive layer located within the active material of the positive electrode or within the active material of the negative electrode is not in physical contact with the current collector of the positive electrode or the current collector of the negative electrode. Optionally, the portion of the first electronic and ion conductive layer located within the active material of the positive electrode or within the active material of the negative electrode is disposed within the active material of the positive electrode or within the active material of the negative electrode by a method selected from the group consisting of: wet processing, dry processing, mechanical pressing, thermal deposition, coating, and any combination of these methods.

[0073] Optionally, the electrochemical cell further comprises a second electronically and ionically conductive layer; wherein the first electronically and ionically conductive layer is positioned in electrical contact with the positive electrode, and wherein the second electronically and ionically conductive layer is positioned in electrical contact with the negative electrode, and wherein the first electronically and ionically conductive layer and the second electronically and ionically conductive layer are not in physical contact or electrical contact with each other.

[0074] Optionally, the first electronically and ionically conductive layer comprises external current collector rods.

[0075] Optionally, the first electronically and ionically conductive layer has an electrical conductivity greater than or equal to 1 S / cm, greater than or equal to 10 S / cm, or greater than or equal to 100 S / cm. Optionally, the first electronically and ionically conductive layer has an electrical conductivity less than or equal to 10 Ω·cm 2 , less than or equal to 5 Ω·cm 2 , less than or equal to 3 Ω·cm 2 , less than or equal to 1 Ω·cm 2 , selected from 0.3 Ω·cm 2 To 3Ω·cm 2 range, selected from 0.03 Ω·cm 2 To 3 Ω·cm 2 range, selected from 0.1 Ω·cm 2 To 10 Ω·cm 2 range, selected from 0.3 Ω·cm 2 To 5 Ω·cm 2range or selected from 0.3 Ω·cm 2 To 3 Ω·cm 2 range of ionic resistance.

[0076] Optionally, the first electronically and ionically conductive layer has a thickness less than or equal to 100 μm, less than or equal to 50 μm, less than or equal to 25 μm, less than or equal to 10 μm, less than or equal to 1 μm, less than or equal to 100 nm, selected from the range of 10 nm to 100 μm, selected from the range of 10 nm to 10 μm, or selected from the range of 50 nm to 5 μm.

[0077] Optionally, the first electronic and ion conductive layer is disposed in physical contact with the separator. Optionally, the first electronic and ion conductive layer is in physical contact with at least 10% of the outer surface of the separator. Optionally, the first electronic and ion conductive layer is in physical contact with the positive electrode or the negative electrode. Optionally, the first electronic and ion conductive layer is in physical contact with at least 10% of the outer surface of the positive electrode or the negative electrode. Optionally, the first electronic and ion conductive layer is at least partially covered by the positive electrode material or the negative electrode material.

[0078] Optionally, the first electronic and ion conductive layer increases the electronic conductivity of at least a portion of the positive electrode or the negative electrode. Optionally, the first electronic and ion conductive layer provides an additional path for electron transfer between the positive electrode and the positive electrode current collector or an additional path for electron transfer between the negative electrode and the negative electrode current collector; the first electronic and ion conductive layer provides a uniform electric field adjacent to the positive electrode and within the positive electrode or a uniform electric field adjacent to the negative electrode and within the negative electrode or any combination of the benefits provided by these. Optionally, the first electronic and ion conductive layer provides an auxiliary path for electrons to or from the positive electrode or the negative electrode. Optionally, the first electronic and ion conductive layer provides a uniform electric field adjacent to the positive electrode or the negative electrode and within the positive electrode or the negative electrode, thereby providing uniform ion deposition into the positive electrode or the negative electrode. In an exemplary embodiment, the first electronic and ion conductive layer prevents dendrite growth on or from the positive electrode or the negative electrode.

[0079] In certain embodiments, the electrochemical cell of this aspect further comprises a second electronically and ionically conductive layer. Optionally, the first electronically and ionically conductive layer is positioned in electrical contact with the positive electrode, and wherein the second electronically and ionically conductive layer is positioned in electrical contact with the negative electrode.

[0080] Optionally, the separator comprises a microporous layer comprising a polymer, polyethylene, polypropylene, polyethylene terephthalate, Kapton, polyester, Nafion, ZrO2, polyimide, polytetrafluoroethylene, a glass separator, a non-woven separator, a woven separator, or any combination thereof. Optionally, the separator comprises a polymer electrolyte, a solid electrolyte, a gel electrolyte, Nafion, ZrO2, PVDF, PEO, PMMA, LISICON, NASICON, LIPON, NaPON, PE, PP, PET, Kapton, or any combination thereof.

[0081] In an embodiment, the separator comprises a high mechanical strength layer. Optionally, the separator comprises a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern. Optionally, the separator further comprises a first ionically conductive and electronically insulating material disposed in at least a portion of the plurality of holes of the first high mechanical strength layer.

[0082] In certain embodiments, for example, a separator includes: a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; and a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern; the second pattern having an offset alignment relative to the first pattern such that an overlap of the holes in the first high mechanical strength layer and the holes in the second high mechanical strength layer along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer is less than or equal to 20%; wherein the first high mechanical strength layer and the second high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer and the second high mechanical strength layer can be transferred through the first high mechanical strength layer and the second high mechanical strength layer.

[0083] Optionally, the separator comprises a coating coated on at least one outer surface of the first electronic and ion conducting layer, at least one surface of the positive electrode, or at least one surface of the negative electrode. Optionally, the separator comprises a film deposited on at least one outer surface of the first electronic and ion conducting layer, at least one surface of the positive electrode, or at least one surface of the negative electrode. Optionally, the first electronic and ion conducting layer is a component of the separator. Optionally, the first electronic and ion conducting layer is a coating on the separator. Optionally, the separator has a total thickness less than or equal to 500 μm or selected from the range of 10 nm to 200 μm.

[0084] Optionally, the positive electrode or the negative electrode comprises an interlayer host material. Optionally, the positive electrode or the negative electrode comprises a material that undergoes a shape change during charge or discharge of the electrochemical cell. Optionally, the positive electrode comprises a metal oxide, sulfur, SO2, lithium-thionyl chloride, MnO2, CF x、CuO、V6O 13 , V2O5, FeS2, CuCl2, I2, HgO, cadmium, bromine, hydrogen-based electrode, oxygen-based electrode, bromine, FeS, V2O5, Ag, Ni, Pb, PbO2, carbon, LiCoO2, LiFePO4, LiMn2O4, carbon-based oxygen cathode, carbon-based water cathode, alkali metal, alkali metal alloy, binary or ternary alkali metal alloy with one or more of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In, zinc oxide, Na, lead oxide, Li, lithium oxide, lithium peroxide, lithium titanium oxide, oxygen active material cathode, water active material cathode, Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, copper hexacyanoferrate, polypyrrole, activated carbon, graphene, graphite, nanocarbon, antimony, alloy of tin and antimony, 5% vanadium-doped lithium iron phosphate, lithium iron fluorophosphate, manganese spinel, lithium nickel manganese cobalt, purpurin, purpurin lithium, lithium vanadate, lithium titanate, cobalt oxide, iron phosphate, titanium dioxide, silicon, copper antimonide, water-soluble gaseous oxidant, water-soluble liquid oxidant, water-soluble solid oxidant or any combination of these. Optionally, the negative electrode includes Si, Li, Zn, ZnO, carbon, Na, Mg, Sn, Cd, Pb, PbO2, LTO, vanadium oxide, alkali metal, alkali metal alloy, binary or ternary alkali metal alloy with one or more of Ca, Mg, Sn, Ag, Zn, Bi, Al, Cd, Ga, In, zinc oxide, Na, lead oxide, Li, lithium oxide, lithium peroxide, lithium titanium oxide, oxygen active material cathode, water active material cathode, Na 2 / 3 [Fe 1 / 2 Mn 1 / 2 ]O2, copper hexacyanoferrate, polypyrrole, activated carbon, graphene, graphite, nanocarbon, antimony, alloy of tin and antimony, 5% vanadium-doped lithium iron phosphate, lithium iron fluorophosphate, manganese spinel, lithium nickel manganese cobalt, purpurogen, purpurogen lithium, lithium vanadate, lithium titanate, cobalt oxide, iron phosphate, titanium dioxide, silicon, SO2, lithium-thionyl chloride, MnO2, CF x 、CuO、V6O 13 , V2O5, FeS2, CuCl2, I2, HgO, cadmium, bromine, hydrogen-based electrodes, oxygen-based electrodes, bromine, copper antimonide, or any combination of these.

[0085] Optionally, the positive electrode comprises an active positive electrode material; and wherein the first electronically and ionically conductive layer is disposed in electrical contact with the active positive electrode material. Optionally, the positive electrode further comprises a current collector in electrical contact with the active positive electrode material. Optionally, the negative electrode comprises an active negative electrode material; and wherein the first electronically and ionically conductive layer is disposed in electrical contact with the active negative electrode material. Optionally, the negative electrode further comprises a current collector in electrical contact with the active negative electrode material.

[0086] Optionally, the electronically and ionically conductive layer comprises an external current collector rod, for example for reduction and / or oxidation. Optionally, the first electronically and ionically conductive layer reduces one of the positive electrode and the negative electrode. Optionally, the external current collector rod oxidizes one of the positive electrode and the negative electrode, such as occurs in oxygen evolution in a metal-air battery.

[0087] In various embodiments, the electrochemical cell comprises a secondary battery, a primary battery, a flow battery, a fuel cell, or a semisolid battery, or an electrolyte capacitor, or a lead-acid battery. Optionally, the electrochemical cell comprises a lithium ion battery, a lithium metal battery, a zinc battery, a lithium-air battery, a zinc-air battery, an aluminum-air battery, an iron-air battery, a lithium-water battery, a silicon-based battery, a sodium battery, a magnesium battery, a sodium ion battery, a magnesium ion battery, an alkaline battery, or a lead-acid battery, or a redox flow battery, or a fuel cell, or an electrolyte capacitor. Optionally, the electrochemical cell comprises a lithium battery comprising one or more of a silicon-based anode, a lithium anode, a metal oxide electrode, a sulfur-based cathode, a carbon-based oxygen cathode, and a carbon-based water cathode.

[0088] In another aspect, an electrochemical cell is provided comprising: a positive electrode; a negative electrode; an ionically conductive and electronically insulating separator positioned between the positive electrode and the negative electrode, wherein the separator comprises: a first high mechanical strength layer having a plurality of pores extending completely through the first high mechanical strength layer and arranged in a first pattern; and a first ionically conductive and electronically insulating material disposed in at least a portion of the plurality of pores in the first high mechanical strength layer; a first electrolyte positioned between the positive electrode and the separator; and a second electrolyte positioned between the negative electrode and the separator; wherein the first electrolyte and the second electrolyte are capable of conducting charge carriers.

[0089] Optionally, the first ion-conducting and electronically insulating material comprises a solid electrolyte, a gel electrolyte, a polymer electrolyte, Nafion, ZrO2, LISICON, NASICON, PEO, Li 10 GeP2S 12 、LIPON、PVDF、Li3N、Li3P、LiI、LiBr、LiCl、LiF、Lithium imide、KOH、NaOH、Perovskite oxide、La 0.5 Li 0.5TiO3, sulfo-LISICON, Li 3.25 Ge 0.25 P 0.75 S4, glass ceramics, Li7P3S 11 , glassy materials, Li2S-SiS2-Li3PO4, lithium nitride, polyethylene oxide, doped Li3N, Li2S-SiS2-Li3PO4, LIPON, Li 14 Zn(GeO4)4, Li-β-alumina, Li 3.6 Si 0.6 P 0.4 O4, Li2S-P2S5, PEO-LiClO4, LiN(CF3SO2)2 / (CH2CH2O)8, NaPON, SiO2, alumina, quartz glass, ceramics, glass ceramics, water-stable polymers, glassy metal ion conductors, amorphous metal ion conductors, ceramic-active metal ion conductors, glass-ceramic-active metal ion conductors, ion-conducting ceramics, ion-conducting solid solutions, ion-conducting glasses, solid lithium ion conductors, or any combination of these.

[0090] Optionally, the first ionically conductive and electronically insulating material occupies 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, or 80% or more by volume of the separator. Optionally, the first ionically conductive and electronically insulating material occupies 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, or 80% or more of the surface area of ​​the separator.

[0091] Optionally, the first ionically conductive and electronically insulating material has an average thickness selected from the range of 0.01 μm to 2000 μm. Optionally, the first ionically conductive and electronically insulating material has an average thickness selected from the range of 0.005 mm to 0.05 mm.

[0092] In an embodiment, the first ionically conductive and electronically insulating material has an average porosity of less than 1% or is non-porous. Optionally, the first ionically conductive and electronically insulating material has an average porosity selected from the range of 0% to 5%. Preferably, the first ionically conductive and electronically insulating material is substantially free of pinholes, cracks, holes, or any combination of these. Preferably, the first ionically conductive and electronically insulating material is substantially defect-free. Optionally, the first ionically conductive and electronically insulating material is doped.

[0093] Optionally, the first ionically conductive and electronically insulating material has a -5 S / cm, greater than or equal to 10 -4 S / cm, greater than or equal to 10-4 S / cm, greater than or equal to 10 -3 S / cm, greater than or equal to 10 -2 S / cm, greater than or equal to 10 -1 S / cm, greater than or equal to 10 S / cm, selected from 10 -7 S / cm to 100 S / cm, selected from 10 -5 S / cm to 10 S / cm, selected from 10 -3 S / cm to 1 S / cm. Optionally, the first ionically conductive and electronically insulating material has an ionic conductivity selected from 10 -7 Ionic conductivity ranges from S / cm to 100 S / cm.

[0094] Optionally, the first ionically conductive and electronically insulating material is disposed into the plurality of pores using a method selected from the group consisting of wet processing, dry processing, mechanical pressing, thermal deposition, coating, and any combination of these methods.

[0095] Optionally, the first ionically conductive and electronically insulating material is disposed into the plurality of pores by pressing the first high mechanical strength layer into the first ionically conductive and electronically insulating material, such that the first ionically conductive and electronically insulating material is disposed in at least a portion of the plurality of pores of the first high mechanical strength layer. Optionally, pressing the first high mechanical strength layer into the first ionically conductive and electronically insulating material occurs during deformation of the first ionically conductive and electronically insulating material. Optionally, pressing the first high mechanical strength layer into the first ionically conductive and electronically insulating material occurs at a temperature of 400° C. or more or 500° C. or more.

[0096] Optionally, the first high mechanical strength layer comprises a mesh or foam. Optionally, the mesh or foam comprises metal, Ni, stainless steel, tin, Al, Cu, alloy, glass, polymer, Kapton, PE, PP, PET, PTFE, PVDF, SiO2, ceramic, alumina, carbon, graphite, nano-carbon or any combination thereof.

[0097] Optionally, the first ionically conductive and electronically insulating material is disposed in substantially all of the plurality of pores of the first high mechanical strength layer. Optionally, the first ionically conductive and electronically insulating material fills all of the plurality of pores of the first high mechanical strength layer.

[0098] Optionally, the first high mechanical strength layer comprises an electrically insulating material. Optionally, the first high mechanical strength layer comprises Kapton, polyethylene, polypropylene, polyethylene terephthalate, poly(methyl methacrylate), a metal coated with a non-conductive material, an alloy coated with a non-conductive material, a polymer, glass, alumina, silicon dioxide, titanium dioxide, and any combination of these. Optionally, the first high mechanical strength layer comprises one or more materials selected from the group consisting of polyacrylic acid (PAA), cross-linked polyethylene (PEX, XLPE), polyethylene (PE), polyethylene terephthalate (PET, PETE), polyphenylene ether (PPE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polylactic acid (PLA), polypropylene (PP), polybutylene (PB), polybutylene terephthalate (PBT), polyamide (PA), polyimide (PI), polycarbonate (PC), polytetrafluoroethylene (PTFE), polystyrene (PS), Polyurethane (PU), polyester (PE), acrylonitrile-butadiene-styrene (ABS), poly(methyl methacrylate) (PMMA), polyoxymethylene (POM), polysulfone (PES), styrene-acrylonitrile (SAN), ethylene-vinyl acetate (EVA), styrene-maleic anhydride (SMA), PVDF, PEO, LIPON, LISICON, tetramethylammonium hydroxide pentahydrate (CH3)4NOH·5H2O, poly(ethylene oxide) (PEO), copolymers of epichlorohydrin and ethylene oxide P(ECH-co-EO) and poly(vinyl alcohol), PEO– PVA-glass fiber polymer electrolyte, zinc sulfide, silica, PVA and PSA, PVA / V6 / PSS; PVAN6 / (PSS+PAA); V6 / PVA / (PSS+PAA); PVM PSS+PAA(35%)) / (PSS+PAA(35%)); (PSS+PAA(35%)) / PVA / (PSS+PAA(35%)); or (PSS+PAA(35%)) / (PVA(10%)+PSS(20% relative to PVA)) / (PSS+PAA (35%)), polyethylene glycol, polypropylene glycol, PEDOT:PSS, SiO2, lithium nitride, NaPON, PVC, glass fiber mat, polybutylene glycol, alkyl-polyethylene glycol, alkyl-polypropylene glycol, alkyl-polybutylene glycol, copolymers thereof, PEO materials, PVA materials, and any combination thereof.

[0099] Optionally, the first pattern of holes provides a first porosity of the first high mechanical strength layer of greater than or equal to 30%, greater than or equal to 50%, greater than or equal to 70%, selected from the range of 30% to 90%, selected from the range of 30% to 70%, or selected from the range of 40% to 60%. Optionally, the first high mechanical strength layer has an average thickness selected from the range of 0.01 μm to 2000 μm. Optionally, the first high mechanical strength layer has an average thickness selected from the range of 0.005 mm to 0.05 mm.

[0100] Optionally, the electrochemical cell of this aspect further comprises a first electronic and ion conductive layer located between the positive electrode and the separator and in electrical contact with the positive electrode, or located between the negative electrode and the separator and in electrical contact with the negative electrode. Optionally, the electrochemical cell of this aspect further comprises a second electronic and ion conductive layer located between the negative electrode and the separator and in electrical contact with the negative electrode, or located between the positive electrode and the separator and in electrical contact with the positive electrode.

[0101] Optionally, the first electronically and ionically conductive layer is a component of the separator. Optionally, the first electronically and ionically conductive layer is arranged to be in physical contact and / or electrical contact with the separator. Optionally, the first electronically and ionically conductive layer comprises a coating on the separator. Optionally, the first electronically and ionically conductive layer is in physical contact and / or electrical contact with the positive electrode or the negative electrode. Optionally, the electronically and ionically conductive layer comprises an external current collector rod. Optionally, the first electronically and ionically conductive layer comprises a coating on the positive electrode or the negative electrode. Optionally, the electronically and ionically conductive layer reduces one of the positive electrode and the negative electrode. Optionally, the external current collector rod oxidizes one of the positive electrode and the negative electrode.

[0102] Optionally, the positive electrode or the negative electrode comprises an interlayer host material. Optionally, the positive electrode or the negative electrode comprises a material that undergoes a shape change during charge or discharge of the electrochemical cell. Optionally, the positive electrode comprises an active positive electrode material and a current collector in electrical contact with the active positive electrode material. Optionally, the negative electrode comprises an active negative electrode material and a current collector in electrical contact with the active negative electrode material.

[0103] Optionally, in the electrochemical cell of this aspect, the separator further comprises a second high mechanical strength layer having a plurality of holes extending completely through the second high mechanical strength layer and arranged in a second pattern, the second pattern having an offset alignment relative to the first pattern, such that the holes of the first high mechanical strength layer and the holes of the second high mechanical strength layer overlap less than or equal to 20% along an axis extending vertically from the first high mechanical strength layer to the second high mechanical strength layer; and wherein the first high mechanical strength layer and the second high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer and the second high mechanical strength layer can be transferred through the first high mechanical strength layer and the second high mechanical strength layer. Optionally, in the electrochemical cell of this aspect, the separator further comprises a second ionically conductive and electrically insulating material disposed in at least a portion of the plurality of holes of the second high mechanical strength layer. Optionally, the first pattern is substantially complementary to the second pattern. Optionally, the first high mechanical strength layer and the second high mechanical strength layer are not in complete physical contact. Optionally, at least portions of the first high mechanical strength layer and the second high mechanical strength layer are separated by a distance selected from the range of 20 nm to 2 mm. Optionally, a second high mechanical strength layer is provided between the first high mechanical strength layer and the negative electrode or the positive electrode.

[0104] Optionally, in the electrochemical cell of this aspect, the separator further comprises a third high mechanical strength layer having a plurality of holes extending completely through the third high mechanical strength layer and arranged in a third pattern, the third pattern having an offset alignment relative to the first pattern or the second pattern, such that the overlap of the holes of the third high mechanical strength layer and the holes of the first high mechanical strength layer or the holes of the second high mechanical strength layer along an axis extending vertically from the third high mechanical strength layer to the first high mechanical strength layer or the second high mechanical strength layer is less than or equal to 20%; and wherein the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer are positioned so that ions of an electrolyte arranged in contact with the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer can be transferred through the first high mechanical strength layer, the second high mechanical strength layer, and the third high mechanical strength layer. Optionally, in the electrochemical cell of this aspect, the separator further comprises a third ionically conductive and electrically insulating material arranged in at least a portion of the plurality of holes of the third high mechanical strength layer. Optionally, the third pattern is substantially complementary to one or more of the first pattern and the second pattern.

[0105] Optionally, in the electrochemical cell of this aspect, the separator further comprises a fourth high mechanical strength layer having a plurality of holes extending completely through the fourth high mechanical strength layer and arranged in a fourth pattern, the fourth pattern having an offset alignment relative to the first pattern, the second pattern, or the third pattern, such that the holes of the fourth high mechanical strength layer overlap with the holes of the first high mechanical strength layer, the holes of the second high mechanical strength layer, or the holes of the third high mechanical strength layer along an axis extending vertically from the fourth high mechanical strength layer to the first high mechanical strength layer, the second high mechanical strength layer, or the third high mechanical strength layer by less than or equal to 20%; and wherein the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer are positioned so that ions of an electrolyte disposed in contact with the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer can be transferred through the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer. Optionally, the separator further comprises a fourth ionically conductive and electrically insulating material disposed in at least a portion of the plurality of holes of the third high mechanical strength layer. Optionally, the fourth pattern is substantially complementary to one or more of the first pattern, the second pattern and the third pattern.

[0106] Optionally, the plurality of pores of at least two high mechanical strength layers are filled with one or more solid electrolytes. Optionally, the plurality of pores of two outer high mechanical strength layers are filled with one or more solid electrolytes, such as the outer high mechanical strength layer positioned adjacent to the positive electrode or the outer high mechanical strength layer positioned adjacent to the negative electrode or both. Optionally, at least one high mechanical strength layer is conductive. Optionally, at least one high mechanical strength layer comprises a 100% ionomer having a conductivity greater than or equal to 5 W·m -1 ·K -1 , greater than or equal to 10 W·m -1 ·K -1 , greater than or equal to 20 W·m -1 ·K -1 , greater than or equal to 50 W·m -1 ·K -1 , greater than or equal to 100 W·m -1 ·K -1 Or greater than or equal to 200 W·m -1 ·K -1 Optionally, at least one high mechanical strength layer (such as an outer high mechanical strength layer positioned adjacent to the positive electrode or an outer high mechanical strength layer positioned adjacent to the negative electrode or both) includes an external current collector rod useful for reducing one of the positive electrode and the negative electrode or oxidizing one of the positive electrode and the negative electrode.

[0107] In various embodiments, the electrochemical cell comprises a secondary battery, a primary battery, a flow battery, an electrolyte capacitor, a semisolid battery, or a fuel cell. Optionally, the electrochemical cell comprises a lithium ion battery, a lithium metal battery, a zinc battery, a lithium-air battery, a zinc-air battery, an aluminum-air battery, an iron-air battery, a lithium-water battery, a silicon-based battery, an alkaline battery, or a lead-acid battery. Optionally, the electrochemical cell comprises a secondary lithium battery comprising a silicon anode, a lithium anode, a metal oxide electrode, a carbon-based oxygen cathode, a carbon-based water cathode, a water cathode, and an air cathode. One or more.

[0108] In another aspect, a method of making a membrane for an electrochemical cell is provided. In an embodiment of this aspect, the method includes the steps of: providing a first high mechanical strength layer having a plurality of holes extending completely through the first high mechanical strength layer and arranged in a first pattern; and disposing a first ionically conductive and electronically insulating material into all or a portion of the plurality of holes in the first high mechanical strength layer.

[0109] Optionally, the first ionically conductive and electrically insulating material is disposed into the plurality of holes using a method selected from the group consisting of: wet processing, dry processing, mechanical pressing, thermal deposition, and any combination of these methods. Optionally, the first ionically conductive and electrically insulating material is disposed into the plurality of holes by pressing the first high mechanical strength layer into the first ionically conductive and electrically insulating material, so that the first ionically conductive and electrically insulating material is disposed in at least a portion of the plurality of holes of the first high mechanical strength layer. Optionally, the method of this aspect further comprises a step of cooling the first high mechanical strength layer and the first ionically conductive and electrically insulating material after pressing. In an embodiment, this cooling step closes one or more cracks in the first ionically conductive and electrically insulating material formed during the pressing step. Optionally, pressing the first high mechanical strength layer into the first ionically conductive and electrically insulating material occurs during deformation of the first ionically conductive and electrically insulating material. Optionally, wherein pressing the first high mechanical strength layer into the first ionically conductive and electrically insulating material occurs at a temperature of 500°C or higher.

[0110] Optionally, the first high mechanical strength layer comprises a mesh or foam. Optionally, the mesh or foam comprises metal, Ni, stainless steel, glass, ceramic, alumina. Optionally, the in-plane pressure on the first ionically conductive and electrically insulating material from the first high mechanical strength layer promotes solid diffusion of ions through the first ionically conductive and electrically insulating material or contributes to uniform ion deposition on the electrode. Optionally, the in-plane pressure on the first ionically conductive and electrically insulating material from the first high mechanical strength layer causes an increased ionic conductivity of the first ionically conductive and electrically insulating material when compared to the ionic conductivity of the first ionically conductive and electrically insulating material without the in-plane pressure. This increase in ionic conductivity arises from the Poisson's ratio effect, in which the in-plane pressure causes an out-of-plane tension, thereby promoting the passage or solid diffusion of ions through the ionically conductive and electrically insulating material.

[0111] Optionally, the first ion-conducting and electronically insulating material comprises a solid electrolyte, a gel electrolyte, a polymer electrolyte, LISICON, NASICON, PEO, Li 10 GeP2S 12 、LIPON、PVDF、Li3N、Li3P、LiI、LiBr、LiCl、LiF、Perovskite oxide、La 0.5 Li 0.5 TiO3, sulfo-LISICON, Li 3.25 Ge 0.25 P 0.75 S4, glass ceramics, Li7P3S 11 , glassy materials, Li2S-SiS2-Li3PO4, lithium nitride, polyethylene oxide, doped Li3N, Li2S-SiS2-Li3PO4, LIPON, Li 14 Zn(GeO4)4, Li-β-alumina, Li 3.6 Si 0.6 P 0.4 O4, Li2S-P2S5, PEO-LiClO4, LiN(CF3SO2)2 / (CH2CH2O)8, NaPON, ZrO2, Nafion, PEDOT:PSS, SiO2, PVC, glass fiber mat, alumina, quartz glass, ceramics, glass ceramics, water-stable polymers, glassy metal ion conductors, amorphous metal ion conductors, ceramic-active metal ion conductors, glass-ceramic-active metal ion conductors, ion-conductive ceramics, ion-conductive solid solutions, ion-conductive glasses, solid lithium ion conductors, or any combination of these.

[0112] Optionally, the first ionically conductive and electronically insulating material comprises 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, or 80% or more by volume of the separator. Optionally, the first ionically conductive and electronically insulating material has an average thickness selected from the range of 0.01 μm to 2000 μm.

[0113] Optionally, the first ionically conductive and electronically insulating material has an average porosity of less than 1%. Preferably, the first ionically conductive and electronically insulating material is non-porous. Optionally, the first ionically conductive and electronically insulating material has an average porosity selected from the range of 0% to 5%. Optionally, the first ionically conductive and electronically insulating material is substantially free of pinholes, cracks, holes, or any combination of these. Optionally, the first ionically conductive and electronically insulating material is substantially defect-free. Optionally, the first ionically conductive and electronically insulating material is doped.

[0114] Optionally, the first ionically conductive and electronically insulating material has a -5 S / cm. Optionally, the first ionically conductive and electronically insulating material has an ionic conductivity selected from 10 -7 Ionic conductivity ranges from S / cm to 100 S / cm.

[0115] Optionally, the first ionically conductive and electronically insulating material is disposed in substantially all of the plurality of pores of the first high mechanical strength layer. Optionally, the first ionically conductive and electronically insulating material fills all of the plurality of pores of the first high mechanical strength layer.

[0116] Optionally, the average thickness of the high mechanical strength layer is selected from the range of 10 nm to 2000 μm. Optionally, the average thickness of the high mechanical strength layer is selected from the range of 0.005 mm to 0.05 mm. Optionally, the first pattern of holes provides a first porosity of the first high mechanical strength layer greater than or equal to 30%. Optionally, the first pattern of holes provides a porosity of the first high mechanical strength layer selected from the range of 30% to 70%.

[0117] Optionally, the first high mechanical strength layer comprises an electrically insulating material, Kapton, polyethylene, polypropylene, polyethylene terephthalate, poly(methyl methacrylate), a metal coated with a non-conductive material, an alloy coated with a non-conductive material, a polymer, glass, ceramics, alumina, silicon dioxide, titanium dioxide, and any combination thereof. Optionally, the first high mechanical strength layer comprises one or more materials selected from the group consisting of polyacrylic acid (PAA), cross-linked polyethylene (PEX, XLPE), polyethylene (PE), polyethylene terephthalate (PET, PETE), polyphenylene ether (PPE), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polylactic acid (PLA), polypropylene (PP), polybutylene (PB), polybutylene terephthalate (PBT), polyamide (PA), polyimide (PI), polycarbonate (PC), polytetrafluoroethylene (PTFE), polystyrene (PS), Polyurethane (PU), polyester (PE), acrylonitrile-butadiene-styrene (ABS), poly(methyl methacrylate) (PMMA), polyoxymethylene (POM), polysulfone (PES), styrene-acrylonitrile (SAN), ethylene-vinyl acetate (EVA), styrene-maleic anhydride (SMA), PVDF, PEO, LIPON, LISICON, tetramethylammonium hydroxide pentahydrate (CH3)4NOH·5H2O, poly(ethylene oxide) (PEO), copolymers of epichlorohydrin and ethylene oxide P(ECH-co-EO) and poly(vinyl alcohol), PEO– PVA-glass fiber polymer electrolyte, zinc sulfide, silica, PVA and PSA, PVA / V6 / PSS; PVAN6 / (PSS+PAA); V6 / PVA / (PSS+PAA); PVM PSS+PAA(35%)) / (PSS+PAA(35%)); (PSS+PAA(35%)) / PVA / (PSS+PAA(35%)); or (PSS+PAA(35%)) / (PVA(10%)+PSS(20% relative to PVA)) / (PSS+PAA (35%)), polyethylene glycol, polypropylene glycol, polybutylene glycol, NaPON, ZrO2, Nafion, PEDOT:PSS, SiO2, PVC, glass fiber mat, alkyl-polyethylene glycol, alkyl-polypropylene glycol, alkyl-polybutylene glycol, their copolymers, PEO materials, PVA materials, Ni, Cu, Al, stainless steel, alumina and any combination thereof.

[0118] Optionally, the first high mechanical strength layer comprises a conductive material, a metal, a metal alloy, a metal mesh, a semiconductor, a metal foam, polyethylene, polypropylene, polyethylene terephthalate, poly(methyl methacrylate), and any combination of these.

[0119] In an embodiment, the first high mechanical strength layer comprises an electrically insulating material and the membrane comprises a separator of an electrochemical cell. In an embodiment, the first high mechanical strength layer comprises an electrically conductive material and the membrane comprises an electronic and ion conductive layer of an electrochemical cell. Optionally, the membrane comprises one or more electronic and ion conductive layers and one or more electrically insulating and ion conductive layers. Optionally, when such a membrane is positioned between a positive electrode and a negative electrode of an electrochemical cell, the membrane provides electrical insulation between the positive electrode and the negative electrode.

[0120] Optionally, the method of this aspect further comprises the step of providing an electronically insulating layer adjacent to the first high mechanical strength layer with a first ionically conductive and electronically insulating material in all or a portion of the plurality of pores of the first high mechanical strength layer.

[0121] Optionally, the method of this aspect further comprises the step of disposing one or more current collectors adjacent to the first high mechanical strength layer in all or a portion of the plurality of pores of the first high mechanical strength layer with a first ionically conductive and electronically insulating material. Optionally, the first current collector is disposed in electrical communication with an active positive electrode material of the electrochemical cell, and the second current collector is disposed in electrical communication with an active negative electrode material of the electrochemical cell.

[0122] In another aspect, an electrochemical cell is provided that includes: a positive electrode; a negative electrode; an ionically conductive and electronically insulating separator positioned between the positive electrode and the negative electrode; one or more thermally and ionically conductive layers positioned between the positive electrode and the separator, or between the negative electrode and the separator; and one or more electrolytes positioned between the positive electrode and the negative electrode; wherein the one or more electrolytes are capable of conducting charge carriers.

[0123] Optionally, the electrochemical cell includes a first thermally and ionically conductive layer located between the positive electrode and the separator and a second thermally and ionically conductive layer located between the negative electrode and the separator.

[0124] Optionally, each of the one or more thermally and ionically conductive layers is arranged to be in thermal communication with the positive electrode or the negative electrode. Optionally, the one or more thermally and ionically conductive layers provide uniform temperature distribution within the electrochemical cell, thereby increasing the performance and life cycle of the electrochemical cell. Optionally, the one or more thermally and ionically conductive layers help provide uniform temperature distribution within the electrochemical cell, thereby increasing the performance and life cycle of the electrochemical cell.

[0125] Optionally, each of the one or more thermally and ionically conductive layers independently has a thickness less than or equal to 0.01 mm or selected from the range of 10 nm to 0.01 mm. Optionally, each of the one or more thermally and ionically conductive layers independently comprises a porous material, a perforated layer, a mesh or a foam. Optionally, each of the one or more thermally and ionically conductive layers independently has a porosity greater than or equal to 50%, greater than or equal to 75%, or greater than or equal to 90%.

[0126] Optionally, each of the one or more thermally and ionically conductive layers independently comprises a metal, an alloy, a ceramic, a polymer, a metal coated with an electrically insulating material, or an alloy coated with an electrically insulating material. Optionally, each of the one or more thermally and ionically conductive layers independently comprises a metal, an alloy, a thermally conductive polymer, a thermally conductive ceramic, a polymer with thermally conductive fibers, a polymer with Al2O3 fibers, Al, Ni, Sn, steel, stainless steel, copper, Si, Li3N, alumina, lithium oxide, lithium peroxide, polyethylene, polypropylene, polyethylene terephthalate, PVDF, Kapton, PTFE, PMMA, NaPON, ZrO2, Nafion, PEDOT:PSS, SiO2, PVC, fiberglass mat, LIPON, or any combination thereof.

[0127] Optionally, each of the one or more thermally and ionically conductive layers independently comprises a mesh. Each of the one or more thermally and ionically conductive layers independently comprises a coating on one or more surfaces of the positive electrode or the negative electrode.

[0128] Optionally, each of the one or more thermally and ionically conductive layers independently comprises a coating on one or more sides of the separator or is positioned adjacent to the separator. Optionally, each of the one or more thermally and ionically conductive layers independently comprises an interior layer of the separator.

[0129] Optionally, for any of the electrochemical cells described herein, any surface of the separator, negative electrode or positive electrode is independently and optionally coated with a hydrophilic material or a hydrophobic material or an anion exchange material or a cation exchange material. Optionally, any layer of the separator, positive electrode or negative electrode independently comprises a hydrophilic material or a hydrophobic material or an anion exchange material or a cation exchange material.

[0130] Optionally, any layer of the separator, positive electrode or negative electrode independently comprises a shape memory material. Optionally, the shape memory material comprises a shape memory alloy, nitinol, a shape memory polymer or any combination thereof. Optionally, the shape memory material layer is pre-stressed prior to operation or cycling of the electrochemical cell.

[0131] In another aspect, an electrochemical cell is provided comprising: a positive electrode; a negative electrode; a solid electrolyte comprising: a first ionically conductive and electrically insulating material; and a set of mechanically tough fibers positioned within the interior of the first ionically conductive and electrically insulating material; wherein the electrolyte is capable of conducting charge carriers. Optionally, the fibers increase the toughness of the solid electrolyte, preventing pinhole cracks during manufacturing and preventing cracks due to cycling.

[0132] Optionally, the fibers are mechanically tough. Optionally, the fibers account for 20% or more by volume of the first ionically conductive and electrically insulating material, or occupy 20% or more of the surface area of ​​the separator. Optionally, the fibers have an average size selected from the range of 0.01 μm to 2000 μm. Optionally, the first ionically conductive and electrically insulating material has an average thickness selected from the range of 0.01 μm to 2000 μm. Optionally, the fibers are ionically insulating. Optionally, the fibers are ionically conductive. Optionally, the fibers are electrically conductive. Optionally, the fibers are electrically insulating.

[0133] For any of the electrochemical cells described herein, the high mechanical strength layer optionally comprises a shape memory material selected from the group consisting of a shape memory alloy, a shape memory polymer, nitinol, and any combination of these. For any of the electrochemical cells described herein, the high mechanical strength layer is optionally conductive. For any of the electrochemical cells described herein, the high mechanical strength layer is optionally electrically insulating. For any of the electrochemical cells described herein, the high mechanical strength layer is optionally mechanically tough. For any of the electrochemical cells described herein, the high mechanical strength layer optionally comprises a shape memory material, or optionally comprises a shape memory alloy, a shape memory polymer, nitinol, and any combination of these. For any of the electrochemical cells described herein, the high mechanical strength layer optionally has a periodic geometry or comprises a mesh. For any of the electrochemical cells described herein, the high mechanical strength layer has a non-periodic geometry or an arbitrary cross-section. For any of the electrochemical cells described herein, the high mechanical strength layer is optionally used to prevent the generation of pinholes during the manufacture of the first ionically conductive and electrically insulating material. For any of the electrochemical cells described herein, the high mechanical strength layer is optionally used to prevent the generation of pinholes during the manufacture of the first ion-conducting and electrically insulating material. For any of the electrochemical cells described herein, the high mechanical strength layer is optionally used to prevent the generation of cracks caused by the diffusion of ions in the first ion-conducting and electrically insulating material. For any of the electrochemical cells described herein, the high mechanical strength layer is optionally partially bonded to the electrode and the first ion-conducting and electrically insulating material. Optionally, the first high mechanical strength layer positions the ion-conducting and electrically insulating material in close contact with the electrode. Optionally, the high mechanical strength layer has shape memory behavior or includes a shape memory alloy, a shape memory polymer or nitinol. Optionally, the first high mechanical strength layer is pre-stressed. For any of the electrochemical cells described herein, the high mechanical strength layer optionally has a 3-dimensional structure or includes a 3-dimensional mesh. Optionally, the high mechanical strength layer is pre-stressed. Optionally, the high mechanical strength layer is pre-stressed to provide physical contact between one or more ion-conducting and electrically insulating materials and the electrode. Optionally, the fibers or web of the electrochemical cell have a binding effect and bind together the ionically conductive and electronically insulating materials.For any of the electrochemical cells described herein, the fibers or web optionally include a polymer or PVDF polymer or rubber.

[0134] Optionally, any separator and / or membrane described herein, such as a single or multilayer separator including a high mechanical strength layer (including multiple holes) is useful for a variety of applications. In an embodiment, any separator and / or membrane described herein is used as a separator for an electrochemical cell. In an embodiment, any separator and / or membrane described herein is used as a liquid filtration membrane. In an embodiment, any separator and / or membrane described herein is used as a gas filtration membrane. In an embodiment, any separator and / or membrane described herein is used as a designed electrode in an electrochemical cell. In an embodiment, any separator and / or membrane described herein is used as a filter for industrial filtration. In an embodiment, any separator and / or membrane described herein is used as a biological filtration membrane. In an embodiment, any separator and / or membrane described herein is used as an industrial filtration membrane in the food industry. In an embodiment, any separator and / or membrane described herein is used as an industrial filtration membrane in the pharmaceutical industry.

[0135] The disclosed separators and membranes are suitable for and / or are optionally used for the concentration and separation of substances through reverse osmosis, ultrafiltration, fine filtration, production of high purity water or high purity chemicals used in the semiconductor industry; collection of effluents from degreasing processes or electrodeposition processes; treatment of waste liquids in various industrial processes (such as papermaking processes, oil-water separation processes, oil emulsion separation processes, etc.); separation and refining of fermentation products; concentration, separation and refining in various food industries, such as concentration of fruit and vegetable juices, processing of soybeans, production of sugar, etc.; medical uses, including artificial kidneys, microfilters for separation of blood components and bacteria, and separators or refiners for medical drugs; biotechnology devices including bioreactors; and electrodes for fuel cells.

[0136] In an embodiment, the invention provides any electrochemical cell as described herein, wherein the electrochemical cell comprises a conductive layer that is not in electrical and / or physical contact with the cathode of the cell, e.g., an electrochemical cell wherein the conductive layer is in electrical and / or physical contact with the anode of the cell.

[0137] In an embodiment, the invention provides an electrochemical cell as described herein, wherein the electrochemical cell comprises a conductive layer that is not in electrical and / or physical contact with the anode of the cell, e.g., an electrochemical cell wherein the conductive layer is in electrical and / or physical contact with the cathode of the cell.

[0138] In an embodiment, the present invention provides an electrochemical cell as described herein, wherein the electrochemical cell comprises a conductive layer in electrical contact and / or physical contact with an electrode that is not a liquid electrode, for example, an electrochemical cell wherein the conductive layer is in electrical contact and / or physical contact with an electrode that is not an air electrode or an oxygen electrode.

[0139] Optionally, in any electrochemical cell described herein, the electrochemical cell does not include any conductive layer in electrical and / or physical contact with the cathode, such as a conductive layer of a separator. Optionally, in any electrochemical cell described herein, the electrochemical cell does not include any conductive layer in electrical and / or physical contact with the positive electrode, such as a conductive layer of a separator.

[0140] Optionally, in any electrochemical cell described herein, the electrochemical cell does not include any conductive layer in electrical and / or physical contact with the anode, such as a conductive layer of a separator. Optionally, in any electrochemical cell described herein, the electrochemical cell does not include any conductive layer in electrical and / or physical contact with the negative electrode, such as a conductive layer of a separator. Optionally, in any electrochemical cell described herein, the metal layer comprises a porous metal layer or a perforated metal layer.

[0141] Optionally, in any electrochemical cell described herein, the electrochemical cell does not include any conductive layer in electrical and / or physical contact with the liquid electrode, such as a conductive layer of a separator. Optionally, in any electrochemical cell described herein, the electrochemical cell does not include any conductive layer in electrical and / or physical contact with the air electrode or oxygen electrode, such as a conductive layer of a separator.

[0142] Without wishing to be bound by any particular theory, there may be discussion herein of beliefs or understandings of underlying principles or mechanisms associated with the invention. It should be recognized that embodiments of the invention may still be effective and useful regardless of the ultimate correctness of any explanation or hypothesis. BRIEF DESCRIPTION OF THE DRAWINGS

[0143] Figure 1 A side perspective view of a multilayer separator system for an electrochemical system is provided, the multilayer separator system comprising a parallel first high mechanical strength layer and a second high mechanical strength layer having complementary patterns of holes, wherein the second pattern of holes has an offset alignment relative to the first pattern such that the holes of the first pattern and the holes of the second pattern do not overlap along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer.

[0144] Figure 2 A side perspective view of a multilayer separator system for an electrochemical system is provided, the multilayer separator system comprising a parallel first high mechanical strength layer and a second high mechanical strength layer having complementary patterns of holes, wherein the second pattern of holes has an offset alignment relative to the first pattern such that the holes of the first pattern and the holes of the second pattern overlap to a selected degree along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer, for example, the selected degree of overlap minimizes or avoids dendrite growth through the separator system.

[0145] Figure 3A schematic diagram is provided showing a cross-sectional view of a multilayer separator system of the present invention having a first patterned high mechanical strength layer and a second patterned high mechanical strength layer separated by an electrolyte-containing layer.

[0146] Figure 4 A schematic diagram showing a cross-sectional view of a multilayer separator system of the present invention having a first patterned high mechanical strength layer, a second patterned high mechanical strength layer, and a third patterned high mechanical strength layer separated by an electrolyte-containing layer is provided.

[0147] Figure 5 A schematic diagram is provided showing a cross-sectional view of a multilayer separator system of the present invention showing the orientation of pores and solid areas of a first patterned high mechanical strength layer and a second patterned high mechanical strength layer separated by an electrolyte-containing layer.

[0148] Figure 6 A schematic diagram is provided showing a cross-sectional view of a multilayer separator system of the present invention showing the orientation of pores and solid areas of a first patterned high mechanical strength layer, a second patterned high mechanical strength layer, and a third patterned high mechanical strength layer separated by electrolyte-containing layers.

[0149] Figure 7 A schematic diagram is provided providing a cross-sectional view of a lithium battery of the present invention comprising a separator system with two patterned high mechanical strength layers having complementary patterns of pores.

[0150] Figure 8 A schematic diagram is provided providing a cross-sectional view of a lithium battery of the present invention comprising a separator system with four patterned high mechanical strength layers having complementary patterns of holes.

[0151] Fig. 9 A schematic diagram is provided providing a cross-sectional view of an electrochemical cell of the present invention comprising a separator system with three patterned high mechanical strength layers having complementary patterns of holes.

[0152] Fig. 10A A schematic diagram is provided providing a cross-sectional view of an electrochemical cell of the present invention comprising a lithium metal anode, a cathode and a separator system comprising three high mechanical strength layers having complementary patterns of pores, two low ionic resistance layers, two electrolyte-containing pores and a frame component.

[0153] Fig. 10B Schematic diagrams are provided providing a cross-sectional view of an electrochemical cell (e.g., useful for lithium-air, lithium-water batteries) having a separator with a protective solid electrolyte, wherein the solid electrolyte conducts desired ions (e.g., Li + ), but is impermeable to water, air, CO2, pollutants, and materials that deteriorate the performance of electrochemical cells.

[0154] Fig. 10C Schematic diagrams are provided providing a cross-sectional view of an electrochemical cell (e.g., useful for lithium-air, lithium-water batteries) having a separator with a protective solid electrolyte, wherein the solid electrolyte conducts desired ions (e.g., Li + ), but is impermeable to water, air, CO2, pollutants, and materials that deteriorate the performance of electrochemical cells.

[0155] Fig. 10D Schematic diagrams are provided that provide a cross-sectional view of an electrochemical cell (e.g., useful for a lithium-sulfur battery) having a separator with a protective solid electrolyte, wherein the solid electrolyte conducts desired ions (e.g., Li + ), but is impermeable to the passage of particles between the cathode and anode which deteriorates the performance of the electrochemical cell.

[0156] Fig. 10E A schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein the conductive side of the separator adjacent to the anode reduces anode loss; for example, by preventing dendrite growth, reducing anode loss, such as in mossy deposits, during cycling and preventing the passage of cathode material to the anode, which interrupts electrical contact between the anode particles and the current collector and deteriorates the performance of the electrochemical cell.

[0157] Fig.10F A schematic diagram providing a cross-sectional view of an electrochemical cell with a separator is provided, wherein the perforated separator sheet and porous layer act as a separator by providing electrical insulation between electrodes while providing ionic connectivity between electrodes via a fluid electrolyte (aqueous or aprotic).

[0158] Figure 10G A schematic diagram is provided providing a cross-sectional view of an electrochemical cell with a separator, wherein the shape memory effect of two high mechanical strength layers results in very good mechanical contact between the separator and the electrodes.

[0159] Fig. 10H Schematic diagrams are provided that provide a cross-sectional view of an electrochemical cell having a separator, wherein the superelasticity and / or shape memory effect of two high mechanical strength layers results in very good mechanical contact between the separator and the electrodes.

[0160] Fig.10I Schematic diagrams are provided that provide a cross-sectional view of an electrochemical cell having a separator, wherein the superelasticity and / or shape memory effect of two high mechanical strength layers results in very good mechanical contact between the separator and the electrodes.

[0161] Fig.10JSchematic diagrams are provided of a cross-sectional view of an electrochemical cell having a separator, wherein the conductive side of the separator reduces anode losses during cycling, such as large deformations of silicon, which disrupt electrical contact between the anode particles and the current collector and deteriorate the performance of the electrochemical cell.

[0162] Figure 10K A schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein the conductive side of the separator near the anode reduces anode losses, such as in large deformations of silicon, during cycling, which interrupt electrical contact between the anode particles and the current collector and deteriorate the performance of the electrochemical cell.

[0163] Fig.10L Schematic diagrams providing cross-sectional views of electrochemical cells are provided.

[0164] Figure 10M Schematic diagrams providing cross-sectional views of electrochemical cells are provided.

[0165] Fig.10N Schematic diagrams providing cross-sectional views of electrochemical cells are provided.

[0166] Fig.10O Schematic diagrams providing cross-sectional views of electrochemical cells are provided.

[0167] Figure 10P Schematic diagrams providing cross-sectional views of electrochemical cells are provided.

[0168] Fig.11A and Fig. 11B Examples of designs of porous patterned layers for some separator systems of the present invention are provided.

[0169] Fig.12 A schematic diagram of a cross-sectional view of an electrochemical cell including a separator system of the present invention is provided.

[0170] Fig.13 A schematic diagram is provided for simplicity to illustrate the desired trajectory of dendrite growth in the electrochemical system of the present invention.

[0171] Fig.14 (Panels AM) provide examples of complementary patterns of holes useful in the patterned high mechanical strength layer of the separator system of the present invention.

[0172] Fig.15 Graphs are provided of the charge and discharge capacity (mAh / g) as a function of the number of cycles for an electrochemical cell having: (A) a multilayer separator system of the present invention having a total thickness of 125 microns, and (B) a Celgard separator having a thickness of 25 microns.

[0173] Fig.16A graph is provided showing the charge and discharge capacity (mAh / g) as a function of the number of cycles for an electrochemical cell having a multilayer separator system of the present invention, a lithium metal anode and a LiCoO2 cathode (A, lines 1, 5 and 6) compared to an electrochemical cell having a conventional separator (B, lines 2 and 3).

[0174] Fig.17 A graph is provided showing the charge and discharge capacity (mAh / g) as a function of the number of cycles for an electrochemical cell having a multilayer separator system of the present invention, a lithium metal anode and a LiCoO2 cathode (lines A, B and C) in comparison to a reference electrode fabricated with perforated Kapton between two Celgard layers (lines F and D) and a Celgard separator having a thickness of 25 microns (lines H and I).

[0175] Fig.18 A schematic diagram is provided showing an electrochemical cell of the present invention having a multilayer separator comprising three high mechanical strength layers having complementary patterns of pores.

[0176] Fig.19 Provides a diagram showing the Fig.18 The Li of the multilayer separator shown + Schematic diagram of the ion trajectories.

[0177] Fig. 20 A graph of cell voltage (V vs. Li) versus cycle time (h) is provided for electrostatic lithium peeled from two symmetrical (5 / 9)" lithium chips separated by a multilayer separator of the present invention.

[0178] Fig.21 Provides graphs of current [mA] versus time [h] and voltage [v] versus time [h].

[0179] Fig. 22 Graphs of current [A] (on top) and voltage [v] (on bottom) versus time [s] are provided in CR2032 cells fabricated with Li metal, LiFePO4 cathodes separated by the multilayer separator of the present invention.

[0180] Fig.23 and Fig.24 Photographs of perforated layers useful in separator systems of some embodiments and experiments are provided.

[0181] Fig.25 , Fig.26 , Fig. 27 and Fig.28 Provided are photographs of perforated layers useful in separator systems of some embodiments.

[0182] Fig.29Cross-sectional views of embodiments of electrochemical cells including composite membranes are provided.

[0183] Fig.30 Various composite membrane embodiments are described.

[0184] Figures 31A-31D Provided before charging ( Fig.31A ) and after ( Fig.31D ), and after multiple charge / discharge cycles ( Fig.31C and Fig.31D ) Schematic cross-section of an electrochemical cell.

[0185] Figure 32-41 Graphs are provided showing experimental data obtained from an electrochemical cell in which ionically and electronically conductive layers are positioned adjacent electrodes.

[0186] Figure 42-47 Schematic cross-sectional views of embodiments of electrochemical cells including one or more conductive layers are provided. Detailed Description

[0187] Generally, the terms and phrases used herein have their art-recognized meanings, which can be found by reference to standard texts, journal references and context known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the present invention.

[0188] With reference to the drawings, like numbers refer to like elements, and like numbers appearing in more than one drawing refer to like elements. In addition, hereinafter, the following definitions apply:

[0189] The term "electrochemical cell" refers to a device and / or device component that converts chemical energy into electrical energy or converts electrical energy into chemical energy. An electrochemical cell has two or more electrodes (e.g., a positive electrode and a negative electrode) and an electrolyte, wherein electrode reactions occurring at the electrode surfaces result in a charge transfer process. Electrochemical cells include, but are not limited to, primary batteries, secondary batteries, and electrolytic systems. In certain embodiments, the term electrochemical cell includes fuel cells, supercapacitors, capacitors, flow batteries, metal-air batteries, and semisolid batteries. General battery and / or battery structures are known in the art, see, for example, U.S. Patent Nos. 6,489,055, 4,052,539, 6,306,540, Seel and Dahn J. Electrochem. Soc. 147(3) 892-898 (2000).

[0190] The term "capacity" is a characteristic of an electrochemical cell and refers to the total amount of charge that an electrochemical cell, such as a battery, can hold. Capacity is generally expressed in units of ampere-hours. The term "specific capacity" refers to the capacity output per unit weight of an electrochemical cell, such as a battery. Specific capacity is generally expressed in ampere-hours kg -1 The unit is expressed as .

[0191] The term "discharge rate" refers to the current flow when an electrochemical cell is discharged. Rate It can be expressed in amperes. Optionally, the discharge Rate It can be normalized to the rated capacity of the electrochemical cell and expressed as C / (Xt), where C is the capacity of the electrochemical cell, X is a variable, and t is a specified time unit as used herein equal to 1 hour.

[0192] "Current density" refers to the current flowing per unit electrode area.

[0193] Electrode refers to an electrical conductor, in which ions and electrons are exchanged with an electrolyte and an external circuit. "Positive electrode" and "cathode" are used synonymously in this description and refer to an electrode with a higher electrode potential (i.e., higher than the negative electrode) in an electrochemical cell. "Negative electrode" and "anode" are used synonymously in this description and refer to an electrode with a lower electrode potential (i.e., lower than the positive electrode) in an electrochemical cell. Cathode reduction refers to the acquisition of electrons of a chemical substance, while anodic oxidation refers to the loss of electrons of a chemical substance. The positive and negative electrodes of the current electrochemical cell may also include a conductive diluent, such as acetylene black, carbon black, powdered graphite, coke, carbon fiber, graphene, and metal powder, and / or may also include a binder, such as a polymer binder. Useful binders for the positive electrode in some embodiments include fluoropolymers, such as polyvinylidene fluoride (PVDF). The positive and negative electrodes of the present invention may be provided in various useful configurations and form factors known in the field of electrochemistry and battery science, including thin electrode designs such as thin film electrode configurations. The electrodes are made as disclosed herein and as known in the art, including as disclosed in, for example, U.S. Patent Nos. 4,052,539, 6,306,540, and 6,852,446. For some embodiments, the electrodes are generally made by depositing a slurry of electrode material, conductive inert material, binder, and liquid carrier onto an electrode current collector and then evaporating the carrier to leave a deposit in electrical contact with the current collector.

[0194] "Electrode potential" refers to the voltage due to the presence of, or contact with, an electrode of a chemical species in a different oxidation (valence) state, usually measured relative to a reference electrode.

[0195] "Electrolyte" refers to an ionic conductor that can be in a solid state, a liquid state (most commonly), or more rarely a gas (eg, a plasma).

[0196] “Standard electrode potential” (E°) refers to the electrode potential when the concentration of the solute is 1 M, the gas pressure is 1 atm, and the temperature is 25 degrees Celsius. As used herein, the standard electrode potential is measured relative to a standard hydrogen electrode.

[0197] "Active material" refers to the material in an electrode that participates in the electrochemical reactions that store and / or transport energy in an electrochemical cell.

[0198] "Cation" refers to a positively charged ion, and "anion" refers to a negatively charged ion.

[0199] "Electrical contact," "electrical communication," "electronic contact," and "electronic communication" refer to the arrangement of one or more objects so that electrical current efficiently flows from one object to another. For example, in some embodiments, two objects having a resistance between them of less than 100Ω are considered to be in electrical communication with each other. Electrical contact may also refer to a component of a device or object used to establish electrical communication, such as an electrical connection, with an external device or circuit. "Electrical communication" also refers to the ability of two or more materials and / or structures to transfer charge between them, such as in the form of transfer of electrons. In some embodiments, the components in electrical communication are in direct electrical communication, where an electrical signal or charge carrier is transferred directly from one component to another. In some embodiments, the components in electrical communication are in indirect electrical communication, where an electrical signal or charge carrier is transferred indirectly from one component to another via one or more intermediate structures, such as circuit elements that separate the components.

[0200] "Thermal contact" and "thermal communication" are used synonymously and refer to the orientation or position of an element or material, such as a current collector or heat transfer rod and a heat sink or heat source, so that there is more efficient heat transfer between the two elements than if the two elements were thermally isolated or insulated. If heat is transmitted much faster between them than if the elements or materials were thermally isolated or insulated, the elements or materials may be considered to be in thermal communication or contact. Two elements in thermal communication or contact may reach a thermal equilibrium or thermally stable state, and in some embodiments may be considered to be in a thermal equilibrium or thermally stable state with each other. In some embodiments, the elements in thermal communication with each other are separated from each other by a thermally conductive material or an intermediate thermally conductive material or a device component. In some embodiments, the elements in thermal communication with each other are separated by a distance of 1 μm or less. In some embodiments, the elements in thermal communication with each other are arranged in physical contact.

[0201] "High mechanical strength" refers to a property of the components of the separator system of the present invention, such as the first high mechanical strength layer, the second high mechanical strength layer, the third high mechanical strength layer, and the fourth high mechanical strength layer having mechanical strength sufficient to prevent physical contact of opposing electrodes, sufficient to prevent short circuits due to external objects within the battery (such as from manufactured metal particles), and sufficient to prevent short circuits due to, for example, dendrite growth between the positive and negative electrodes of the electrochemical cell during the charge and discharge cycles of the secondary electrochemical cell. In an embodiment, for example, the high mechanical strength layer has mechanical strength sufficient to prevent puncture due to external objects in the battery (such as from manufactured metal particles) and short circuits due to the growth of dendrites between the electrodes. In an embodiment, for example, the high mechanical strength layer has mechanical strength sufficient to prevent short circuits between the positive and negative electrodes of the electrochemical cell due to external objects in the battery (such as from manufactured metal particles) and short circuits due to the growth of dendrites between the electrodes. In an embodiment, for example, the high mechanical strength layer is characterized by a Young's modulus greater than or equal to 500 MPa, and optionally for some applications a Young's modulus greater than or equal to 1 GPa, and optionally for some applications a Young's modulus greater than or equal to 10 GPa, and optionally for some applications a Young's modulus greater than or equal to 100 GPa. In an embodiment, for example, the high mechanical strength layer is characterized by a yield strength greater than or equal to 5 MPa, and optionally for some applications a yield strength greater than or equal to 50 MPa, and optionally for some applications a yield strength greater than or equal to 100 MPa, and optionally for some applications a yield strength greater than or equal to 500 MPa. In an embodiment, for example, the high mechanical strength layer is characterized by a propagation tear strength greater than or equal to 0.005 N, and optionally for some applications a propagation tear strength greater than or equal to 0.05 N, a propagation tear strength greater than or equal to 0.5 N, a propagation tear strength greater than or equal to 1 N. In an embodiment, for example, the high mechanical strength layer is characterized by an initiated tear strength of greater than or equal to 10 N, and optionally for some applications, an initiated tear strength of greater than or equal to 100 N. In an embodiment, for example, the high mechanical strength layer is characterized by a tensile strength of greater than or equal to 50 MPa, and optionally for some applications, a tensile strength of greater than or equal to 100 MPa, and optionally for some applications, a tensile strength of greater than or equal to 500 MPa, and optionally for some applications, a tensile strength of greater than or equal to 1 GPa. In an embodiment, for example, the high mechanical strength layer is characterized by an impact strength of greater than or equal to 10 Ncm, and optionally for some applications, an impact strength of greater than or equal to 50 N cm, and optionally for some applications, an impact strength of greater than or equal to 100 N cm, and optionally for some applications, an impact strength of greater than or equal to 500 N cm.

[0202] "Chemically resistant" refers to the property of the separators and components of the electrochemical system of the present invention, such as layers, in which there is no significant chemical or electrochemical reaction of the battery active materials (such as electrodes and electrolytes). In certain embodiments, chemically resistant also refers to the property in which the tensile retention and elongation retention are at least 90% in the working environment of the electrochemical system, such as an electrochemical cell.

[0203] "Thermally stable" refers to the property of the separators and components of the electrochemical system of the present invention, such as layers, in which there are no significant chemical or electrochemical reactions due to the normal and operational thermal behavior of the cell. In certain embodiments, thermally stable also refers to materials in which the melting point is greater than 100 degrees Celsius, and preferably greater than 300 degrees Celsius for some embodiments, and optionally the coefficient of thermal expansion is less than 50 ppm / degree Celsius. In embodiments, thermally stable refers to the property of a component of the separator system such that it can perform in a rechargeable electrochemical cell without undergoing dimensional or shape changes at temperatures that significantly reduce the performance of the electrochemical cell.

[0204] "Porosity" refers to the amount of a material or component, such as a high mechanical strength layer, corresponding to micropores, such as pores, channels, interstices, etc. Porosity can be expressed as a percentage of the volume of a material, structure, or device component, such as a high mechanical strength layer, corresponding to micropores, such as pores, channels, interstices, etc., relative to the total volume occupied by the material, structure, or device component.

[0205] A separator system for an electrochemical system is provided, which provides electronic, mechanical and chemical properties useful for a range of electrochemical storage and conversion applications. For example, certain embodiments provide structural, physical and electrostatic properties useful for managing and controlling dendrite formation in lithium and zinc-based batteries or flow batteries. Some of the disclosed separator systems include multilayer, porous geometries that support excellent ion transfer properties while providing barriers that effectively prevent mechanical failure, short circuits and / or thermal runaway caused by dendrites. For example, certain embodiments provide structural, physical and electrostatic properties useful for improving the cycle life and rate performance of electrochemical cells such as silicon anode-based batteries or air cathode-based batteries or redox flow batteries or semi-solid batteries. The disclosed separator system includes a multilayer, porous geometries that support excellent ion transfer properties while providing auxiliary paths that effectively increase the electronic conductivity of the electrode or improve the uniformity of the electric field. For example, certain embodiments provide structural, physical and electrostatic properties useful for improving the cycle life and rate performance of electrochemical cells (such as Li-air batteries or fuel cells or flow batteries or semi-solid batteries) of systems based on solid electrolytes. The disclosed separator systems include composite solid electrolyte / support mesh systems and solid electrolyte / support fiber systems that provide the hardness and safety of a solid electrolyte with the toughness and long life of a support mesh or fiber that is useful in the manufacture and operation of thin solid electrolytes without manufacturing pinholes and without operational cracks that occur in conventional solid electrolytes.

[0206] The separators and membranes introduced herein are suitable for use in the concentration and separation of substances through, for example, reverse osmosis, ultrafiltration, fine filtration, production of high-purity water or high-purity chemicals in the semiconductor industry; collection of effluents from degreasing processes or electrodeposition processes; treatment of waste liquids in various industrial processes (such as papermaking processes, oil-water separation processes, oily emulsion separation processes, etc.); separation and refining of fermentation products; concentration, separation and refining in various food industries, such as concentration of fruit and vegetable juices, processing of soybeans, production of sugar, etc.; medical uses, such as artificial kidneys, microfilters for separation of blood components and bacteria, and separators or refiners for medical drugs; biotechnological devices such as bioreactors; and electrodes for fuel cells.

[0207] Figure 1 A side perspective view of a multilayer separator system 100(1) for an electrochemical system is provided, the multilayer separator system 100(1) comprising a parallel first high mechanical strength layer and a second high mechanical strength layer having complementary patterns of apertures, wherein the second pattern of apertures has an offset alignment relative to the first pattern such that the apertures of the first pattern and the apertures of the second pattern do not overlap along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer. Figure 1As shown, separator system 100(1) includes: a first high mechanical strength layer 102(1) having a first pattern including a plurality of holes, such as 104(1) and 104(4); and a second high mechanical strength layer 102(2) having a second pattern including a second plurality of holes, such as 104(2) and 104(3). The first layer and the second layer are characterized by planar geometries and lateral dimensions, such as height H, length L, and width or thickness W. Figure 1 As shown, the holes 104 extend completely through the thickness of the first high mechanical strength layer 102(1) or the second high mechanical strength layer 102(2). Each hole 104 is also characterized by lateral dimensions such as a height h, a length l, and a width or thickness (not shown).

[0208] The superposition of the pattern of the first high mechanical strength layer 102(1) onto the second high mechanical strength layer 102(2) is schematically illustrated as a plurality of offset dashed areas 106(1) on the second high mechanical strength layer 102(2), while the superposition of the pattern of the second high mechanical strength layer 102(2) onto the first high mechanical strength layer 102(1) is schematically illustrated as a plurality of offset dashed areas 106(2) on the first high mechanical strength layer 102(1). Figure 1 In the illustrated embodiment, the first pattern and the second pattern resemble a checkerboard pattern, for example, where the first pattern corresponds to black squares and the second pattern corresponds to red squares of the checkerboard. However, as will be apparent to one skilled in the art, other patterns such as honeycomb patterns, dense circular patterns, brick patterns, triangular patterns, and the like are possible, provided that the first pattern and the second pattern have an offset alignment relative to one another, such as such that the overlap of the holes 104 along an axis extending vertically from the first high mechanical strength layer 102 (1) to the second high mechanical strength layer 102 (2) is less than or equal to 50%, 40%, 30%, 20%, 10%, 5%, 2%, or 0%. Figure 1 In the illustrated embodiment, there is no overlap between the first pattern of holes and the second pattern of holes along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer. Figure 1The arrows 108(1) and 108(2) shown are provided to illustrate the region of non-overlapping apertures along an axis extending vertically from the first high mechanical strength layer 102(1) to the second high mechanical strength layer 102(2). The offset alignment of the first pattern of apertures of the first high mechanical strength layer and the second pattern of apertures of the second high mechanical strength layer prevents dendrite growth through the combination of the first high mechanical strength layer and the second high mechanical strength layer, for example, by mechanically impeding dendrite growth and / or requiring a path involving a tortuous trajectory that is thermodynamically and / or kinetically unfavorable. For example, a dendrite may only pass through the aperture 104(3) of the second high mechanical strength layer 102(2), as shown by arrow A, because it is physically blocked by the first high mechanical strength layer 102(1) at point 110(1). Similarly, a dendrite may only pass through the aperture 104(4) of the first high mechanical strength layer 102(1), as shown by arrow B, because it is physically blocked by the second high mechanical strength layer 102(2) at point 110(2).

[0209] Figure 2 A side perspective view of a multilayer separator system 100(2) for an electrochemical system is provided, the multilayer separator system 100(2) comprising a parallel first high mechanical strength layer and a second high mechanical strength layer having complementary patterns of apertures, wherein the second pattern of apertures has an offset alignment relative to the first pattern such that there is a selected degree of overlap of the apertures of the first pattern and the apertures of the second pattern along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer. Figure 2 As shown, separator system 100 (2) includes: a first high mechanical strength layer 102 (3) having a first pattern including a plurality of holes, such as 104 (5) and 104 (9); and a second high mechanical strength layer 102 (4) having a second pattern including a second plurality of holes, such as 104 (6), 104 (7) and 104 (8). The first high mechanical strength layer and the second high mechanical strength layer 102 are characterized by lateral dimensions, such as height H, length L and width or thickness W. Figure 1 As shown, the holes 104 extend completely through the thickness of the first high mechanical strength layer 102(3) or the second high mechanical strength layer 102(4). Each hole 104 is also characterized by lateral dimensions such as height h, length l, and width or thickness (not shown).

[0210] The superposition of the first pattern of the first high mechanical strength layer 102 (3) to the second high mechanical strength layer 102 (4) is schematically shown as a plurality of dashed areas 106 (3) on the second high mechanical strength layer 102 (4), while the superposition of the second pattern of the second high mechanical strength layer 102 (4) to the first high mechanical strength layer 102 (3) is schematically shown as a plurality of dashed areas 106 (4) on the first layer 102 (3). Figure 2In the illustrated embodiment, the first pattern and the second pattern have an offset alignment relative to each other such that the holes 104 have a selected overlap along an axis extending vertically from the first high mechanical strength layer 102 (3) to the second high mechanical strength layer 102 (4). In embodiments, for example, the selected overlap is less than or equal to 50%, 40%, 30%, 20%, 10%, 5%, or 2%. Figure 2 In the illustrated embodiment, the overlap of the first pattern of holes and the second pattern of holes along an axis extending perpendicularly from the first high mechanical strength layer to the second high mechanical strength layer is greater than zero. Figure 2 The arrows shown are provided to illustrate an overlapping region 112 of holes and a region of holes that do not overlap along an axis extending vertically from the first high mechanical strength layer 102(3) to the second high mechanical strength layer 102(4). The offset alignment of the pattern of holes of the first high mechanical strength layer and the pattern of holes of the second high mechanical strength layer prevents dendrite growth through the combination of the first high mechanical strength layer and the second high mechanical strength layer, for example, by preventing dendrite growth and / or requiring a passage involving a tortuous trajectory that is thermodynamically and / or kinetically unfavorable.

[0211] The present invention can be further understood by reference to the following non-limiting examples.

[0212] Example 1: Novel separators for electrochemical and chemical systems, for example for batteries such as for rechargeable lithium batteries and in particular for preventing dendrite shorting in Li metal batteries Figure 3 A schematic diagram is provided showing a cross-sectional view of a multilayer separator system of the present invention having first and second high mechanical strength layers (layers R and F) having complementary patterns of pores separated by an electrolyte-containing layer (layer M). Figure 4 A schematic diagram is provided showing a cross-sectional view of a multilayer separator system of the present invention having a first high mechanical strength layer, a second high mechanical strength layer, and a third high mechanical strength layer (layers R and F) having complementary patterns of pores separated by an electrolyte-containing layer (layer M). Figure 3 and 4 In, layer (R) and layer (F) are high mechanical strength layers having a pattern of holes that, when provided in combination, prevent dendrite growth through the separator system, for example when incorporated into an electrochemical system such as an electrochemical cell. Figure 3 and 4In the embodiment, the electrolyte-containing layer M is disposed between layers F and R, and in some embodiments, the electrolyte-containing layer M is preferably thicker than layers F and R. In the electrochemical system, for example, layer M acts as a reservoir for the electrolyte. In the electrochemical system, for example, layer M acts as a separator, thereby preventing electrical and / or physical contact between the positive electrode and the negative electrode while allowing ion transfer between the positive electrode and the negative electrode, so that the electrochemical cell can experience effective discharge and charge characteristics. In an embodiment, for example, layer M is a low ionic resistance layer, such as a conductive microporous membrane. In an embodiment, for example, layer M is a polyethylene (PE) film or a polypropylene (PP) film or a combination of both.

[0213] In some embodiments, the high mechanical strength layers F and R act to prevent dendrite growth in the electrochemical cell to prevent electrical short circuits, thermal runaway, and / or mechanical failure of the cell. As an example, the high mechanical strength layers F and R can be configured to prevent short circuits and capacity loss in lithium metal batteries by preventing dendrite growth between the positive electrode and the negative electrode. In some embodiments, the high mechanical strength layers F and R provide complementary barriers, each having a mechanical strength sufficient to prevent puncture or mechanical failure of the barrier when in contact with growing dendrites.

[0214] In some embodiments, the high mechanical strength layers F and R are provided with complementary patterns of holes extending through the entire thickness of the layers. Figure 5 A schematic diagram is provided showing a cross-sectional view of a multilayer separator system of the present invention, showing pores (schematically shown as dashed areas) and solid areas (schematically shown as filled areas) of a first high mechanical strength layer and a second high mechanical strength layer separated by one or more low ionic resistance layers, such as an electrolyte-containing layer M. Figure 6A schematic diagram is provided showing a cross-sectional view of a multilayer separator system of the present invention, showing pores and solid regions of a first high mechanical strength layer, a second high mechanical strength layer, and a third high mechanical strength layer separated by one or more low ionic resistance layers, such as an electrolyte-containing layer M. As an example, the high mechanical strength layer F can be characterized by a first preselected pattern of pores and solid regions, and the high mechanical strength layer R can be characterized by a second preselected pattern of pores and solid regions that is different from the preselected pattern of the high mechanical strength layer F. In an embodiment, for example, the two patterns are complementary, such that each of the high mechanical strength layers F and R has pores (e.g., through-holes, nanopores, micropores, channels, etc.) that allow ions and electrolytes to be transferred from either side of the high mechanical strength layer, but the alignment of the high mechanical strength layers F and R in the multilayer separator system geometry provides, for example, pores of the high mechanical strength layer F that match the solid regions of the high mechanical strength layer R along an axis extending vertically from the high mechanical strength layer R to the high mechanical strength layer F and solid regions of the high mechanical strength layer F that match the pores of the high mechanical strength layer R. In an embodiment, for example, the holes of the high mechanical strength layers F and R are offset relative to each other so that when they are arranged in combination, for example in parallel or concentric directions, no straight line can pass through the holes of the two layers F and R. This spatial arrangement can be visualized, for example, by considering a periodic pattern, such as a chessboard with white and black squares, wherein the white squares correspond to the holes, and wherein the black squares correspond to the solid areas of the high mechanical strength layer. In an example, the high mechanical strength layer F can be in the form of a general chessboard, and the high mechanical strength layer R can be in the form of an inverted chessboard, a staggered chessboard, wherein the white blocks (corresponding to the holes) are at the location of the black squares (solid parts of layer F), and the black blocks (corresponding to the solid areas) are at the location of the white squares (holes of layer F). This offset alignment results in at least two high mechanical strength layers, wherein when arranged in a multilayer geometry, all holes are blocked by the solid areas of the adjacent layers.

[0215] Placing a low ionic resistance layer M (a typical separator) between high mechanical strength layers F and R provides a separator system that prevents unwanted growth of dendrites extending through the separator system. However, in order to minimize the effect of the separator system on the resistance of the battery, it is desirable in some embodiments to minimize the thickness of high mechanical strength layers F and R while maintaining at least the thickness necessary to provide sufficient mechanical strength to block growing dendrites.

[0216] In an embodiment, for example, the high mechanical strength layers F and R are very thin (e.g., a thickness of less than or equal to 100 μm and optionally a thickness of less than or equal to 20 μm for some embodiments), and thus may optionally be in the form of one or more coatings on the front and / or back side of layer M. The volume fraction and surface fraction of pores in the high mechanical strength layers F and R are selected for a given application, and for some applications, preferably at least a quarter and optionally half of the surface-volume comprises pores and the remainder comprises impermeable solid areas. In an embodiment, the high mechanical strength layers F and R comprise a material that does not react with other components of the electrochemical cell and is chemically resistant and thermally stable. In an embodiment, the high mechanical strength layers F and R comprise an electrical insulator.

[0217] In a specific embodiment useful for lithium metal batteries, the high mechanical strength layers F and R include polyethylene films or polyimide films or polyester films or polypropylene films or Teflon or a mixture of these materials, which have complementary patterns that allow ions and electrolytes to pass through the pores but prevent current from passing directly between the positive electrode and the negative electrode of the electrochemical cell. In an embodiment, for example, the low ionic resistance layer M is a porous polyethylene film or a porous polypropylene film or a mixture of these. In an embodiment, the low ionic resistance layer M has a thickness selected from the range of 10 nm to 200 μm, selected from the range of 80 μm to 120 μm, or selected from the range of 5 μm to 25 μm, and the high mechanical strength layers F and R each independently have a thickness selected from the range of 5 μm to 200 μm, selected from the range of 10 μm to 30 μm, or selected from the range of 5 μm to 30 μm. In an embodiment, the high mechanical strength layers F and R have complementary periodic patterns of pores and solid areas, wherein one or more lateral dimensions of the unit cells characterizing the pores and / or solid areas are selected, for example, in the range of 1 micron and 1 millimeter, preferably 10-30 microns for some applications. Smaller sizes of lateral dimensions of the unit cells of pores as small as 10 times the average pore size of layer R are preferred for some embodiments; but recognizing that there may be practical advantages of larger pores with respect to manufacturing, there may be a compromise in the choice of the physical size of the pores.

[0218] As will be apparent to one skilled in the art, the composition, physical dimensions (e.g., thickness), and mechanical properties (e.g., porosity) of the components of the separator system may depend on the type of electrochemical or chemical battery and / or application. In an embodiment, for example, a separator system for a lead-acid battery may use a thicker, high mechanical strength layer with a larger pore size than in a separator system for a lithium metal battery.

[0219] Apart from Figure 3 and 5In addition to the RMF and FMRMF systems shown in FIG, other separator geometries are useful for some applications. As an example, the present invention includes multilayer systems having 3, 4, 5, 6, 7, 8 high mechanical strength layers, etc., having a pattern of holes selected to prevent dendrite growth. For example, corresponding to Figure 4 and 6 Multilayer systems of the FMRMF system shown having more than two high mechanical strength layers are preferred for some applications because they can be configured to effectively prevent the growth of dendrites from the positive electrode to the negative electrode, yet the added resistance to the battery can still be maintained low enough to provide useful discharge and charge performance.

[0220] As an example, the high energy rechargeable lithium battery of the present invention comprises: (1) an anode comprising lithium metal or lithium alloy, or lithium metal and / or lithium alloy or zinc metal or ZnO or zinc alloy or a mixture of silicon and another material; (2) a cathode; (3) a separator system of the present invention arranged between the anode and the cathode; and (4) one or more electrolytes in ionic communication, optionally physical contact, with the anode and the cathode via the separator. In an embodiment, for example, the electrolyte is a solid, a gel, or a liquid (e.g., a fluid). In some embodiments, the electrode is a solid material or a semi-solid particle (e.g., a small solid particle in a liquid), such as what is used in a semi-solid battery or in a flow battery or in a flow battery. The cross-sectional geometry of the separator system can be a variety of shapes including rectangular, circular, square, etc.

[0221] Figure 7 A schematic diagram is provided that provides a cross-sectional view of a lithium battery of the present invention, the lithium battery including a separator system with two high mechanical strength layers having complementary patterns of pores. The electrochemical cell includes an anode (e.g., lithium metal) and a cathode separated by a multilayer separator system including an electrolyte reservoir. The multilayer separator includes two high mechanical strength layers having complementary patterns of pores separated by a low ionic resistance layer, such as an electrolyte-containing separator and / or a separator. In addition, a very porous medium is disposed between the high mechanical strength layers and the anode and cathode components. As shown in FIG. Figure 7 As shown, the high mechanical strength layer has a pattern including alternating holes and solid areas (e.g., in Figure 7 , the filled areas correspond to solid areas of the high mechanical strength layer, while the dashed areas correspond to holes extending through the high mechanical strength layer). In the illustrated embodiment, the high mechanical strength layers have complementary patterns of holes capable of preventing the growth of dendrites between the cathode and the anode, wherein open areas (e.g., holes) of a first high mechanical strength layer correspond to solid areas of a second high mechanical strength layer along an axis extending perpendicularly from the layers, as shown. Figure 7 shown.

[0222] Figure 8-1 0 provides examples of other embodiments of lithium batteries illustrating additional device configurations and device components of the present invention. Figure 8 A schematic diagram is provided providing a cross-sectional view of a lithium battery of the present invention, the lithium battery comprising a separator system with four high mechanical strength layers having complementary patterns of pores. Figure 8 In the device shown, the high mechanical strength layer R is arranged in direct physical contact with the anode, and the high mechanical strength layer L is arranged in direct physical contact with the cathode. Figure 8 In the embodiment shown, two layers R have the same pattern of holes, and two layers F have the same pattern of holes. The patterns in layers R and F together comprise complementary patterns that eliminate any direct linear pathway between the anode and cathode along an axis extending perpendicularly from the cathode to the anode, thereby preventing dendrite growth-related shorting. Figure 8 In the embodiment shown, the high mechanical strength layer R is arranged in physical contact with the anode to allow ions to pass through layer R and interact with the anode surface; and the high mechanical strength layer F is arranged in physical contact with the cathode to allow ions to pass through layer F and interact with the cathode surface.

[0223] Fig. 9 A schematic diagram is provided providing a cross-sectional view of an electrochemical cell of the present invention comprising a separator system with three high mechanical strength layers having complementary patterns of pores. Fig. 9 In the device shown, a very porous layer (e.g., porosity ≥ 80%) is provided between the high mechanical strength layer F and the anode, and a very porous layer (e.g., porosity ≥ 80%) is provided between the high mechanical strength layer F and the cathode. Fig. 9 In the device shown, the high mechanical strength layer R has a pattern of holes that is complementary to the pattern of holes of the high mechanical strength layer F, and a porous layer (e.g., porosity ≥ 50%) is disposed between the high mechanical strength layer R and the high mechanical strength layer F. In an embodiment, for example, both high mechanical strength layers F feature the same pattern of holes. Fig. 9 In the embodiment shown, both layers F have the same pattern of holes. The patterns in layer R and both layers F together comprise a complementary pattern that eliminates any direct linear path between the anode and cathode along an axis extending perpendicularly from the cathode to the anode, thereby preventing dendrite growth-related shorting. Fig. 9 In the illustrated embodiment, a very porous layer (e.g., porosity ≥ 80%) is configured to be in physical contact with the anode so as to allow ions to pass through the porous layer and interact with the anode surface; and a very porous layer (e.g., porosity ≥ 80%) is configured to be in physical contact with the cathode so as to allow ions to pass through the porous layer and interact with the cathode surface.

[0224] Fig. 10AA schematic diagram is provided that provides a cross-sectional view of an electrochemical cell of the present invention, the electrochemical cell comprising a lithium metal anode, a cathode, and a separator system comprising three high mechanical strength layers having complementary patterns of holes, two low ionic resistance layers, two electrolyte-containing pores, and a frame component. In some embodiments, for example, the frame layer provides a means for physically integrating, connecting, and / or mechanically supporting the components of the total multilayer arrangement. In the lithium battery shown in FIG10, the electrolyte-containing pores are disposed between the anode and the first high mechanical strength layer having a pattern of holes, and the electrolyte-containing pores are disposed between the cathode and the second high mechanical strength layer having a pattern of holes. In some embodiments, for example, the merging of electrolyte-containing pores between the electrode and the high mechanical strength layer is useful to avoid reducing the electrode surface area in order to utilize the useful discharge and charging characteristics of the battery. In the device shown in FIG10, the high mechanical strength layer R has a pore pattern complementary to the pore pattern of the high mechanical strength layer F, and the low ionic resistance layer (e.g., a porosity of ≥ 50%) is disposed between the high mechanical strength layer R and the high mechanical strength layer F.

[0225] Fig. 10B Schematic diagrams are provided providing a cross-sectional view of an electrochemical cell (e.g., useful for lithium-air, lithium-water batteries) having a separator with a protective solid electrolyte, wherein the solid electrolyte conducts desired ions (e.g., Li + ), but impermeable to water, air, CO2, pollutants and materials that deteriorate the performance of the electrochemical cell. The electrochemical cell comprises an anode such as a lithium anode; a cathode such as a carbon-water cathode or a carbon-air cathode; a separator system comprising two high mechanical strength layers with complementary patterns of pores, three low ionic resistance layers and a solid electrolyte layer such as a LISICON layer. Fig. 10B In the device shown, the high mechanical strength layer is an optionally chemically resistant and thermally stable perforated layer that is also electrically insulating, such as a perforated Kapton layer. The use of a complementary high mechanical strength layer comprising Kapton is useful in some embodiments to prevent dendrite growth. Fig. 10B As shown, a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode. Fig. 10BAs shown, a solid electrolyte layer, such as a LISICON layer, is disposed between the third low ionic resistance layer and the cathode, so that ions can be transferred to the cathode surface. In an embodiment, for example, the solid electrolyte layer is disposed in physical contact with the surface of the cathode. In some embodiments, the incorporation of a solid electrolyte layer (e.g., a LISICON layer) is useful for protecting the cathode, such as preventing unwanted chemical reactions with the cathode surface and components of the electrochemical cell, such as electrolyte components other than the solid electrolyte. In some embodiments, the solid electrolyte layer (e.g., a LISICON layer) provides a chemical barrier layer that separates a first side of an electrochemical cell having a first electrolyte from a second side of an electrochemical cell having a second electrolyte different from the first electrolyte. Embodiments of this aspect can therefore provide a means for combining two separate electrolytes, each of which is particularly suitable for selected anode and cathode compositions.

[0226] Fig. 10C Schematic diagrams are provided providing a cross-sectional view of an electrochemical cell (e.g., useful for lithium-air, lithium-water batteries) having a separator with a protective solid electrolyte, wherein the solid electrolyte conducts desired ions (e.g., Li + ), but is impermeable to water, air, CO2, pollutants and materials that deteriorate the performance of the electrochemical cell. The electrochemical cell comprises a lithium anode; a cathode such as a carbon-water cathode or a carbon-air cathode; a separator system comprising two high mechanical strength layers with complementary patterns of pores, three low ionic resistance layers and a solid electrolyte layer such as a LISICON layer. Fig. 10C The overall electrochemical cell geometry in Fig. 10B The overall electrochemical cell geometry shown, wherein a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode, and wherein a solid electrolyte layer, such as a LISICON layer, is disposed between the third low ionic resistance layer and the cathode, so that ions can be transferred to the cathode surface. However, in Fig. 10C In an electrochemical cell of the invention, the high mechanical strength layer is a perforated metal layer having a complementary pattern of holes useful in some embodiments for preventing dendrite growth and reducing anode loss, such as in mossy deposits. Fig. 10BAs discussed above, the incorporation of a solid electrolyte layer (e.g., a LISICON layer) is useful for protecting the cathode, e.g., from unwanted chemical reactions with the cathode surface and components of the electrochemical cell, such as electrolyte components other than the solid electrolyte. In some embodiments, the solid electrolyte layer (e.g., a LISICON layer) provides a chemical barrier layer that separates a first side of the electrochemical cell having a first electrolyte from a second side of the electrochemical cell having a second electrolyte different from the first electrolyte, and thus can provide a means for combining two separate electrolytes, each of which is particularly suitable for selected anode and cathode compositions.

[0227] Fig. 10D Schematic diagrams are provided that provide a cross-sectional view of an electrochemical cell (e.g., useful for a lithium-sulfur battery) having a separator with a protective solid electrolyte, wherein the solid electrolyte conducts desired ions (e.g., Li + ), but is impermeable to the passage of particles between the cathode and the anode which deteriorates the performance of the electrochemical cell. The electrochemical cell comprises an anode, such as a lithium anode; a cathode, such as a sulfur-based cathode; a separator system comprising two high mechanical strength layers with complementary patterns of pores, three low ionic resistance layers and a solid electrolyte layer, such as a LISICON layer. Fig. 10C The overall electrochemical cell geometry in Fig. 10B and 10C The overall electrochemical cell geometry shown, wherein a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode, and wherein a solid electrolyte layer, such as a LISICON layer, is disposed between the third low ionic resistance layer and the cathode, so that ions can be transferred to the cathode surface. However, in Fig. 10D In an electrochemical cell, the high mechanical strength layer is a perforated metal layer having a complementary pattern of holes, and the cathode is optionally a sulfur-based cathode. The incorporation of a high mechanical strength metal layer in the current separator is useful in some embodiments to prevent dendrite growth, reduce anode loss, such as in mossy deposits, and prevent the passage of cathode particles to the anode. Similar to the incorporation of Fig. 10BAs discussed above, the incorporation of a solid electrolyte layer (e.g., a LISICON layer) is useful for protecting the cathode, e.g., from unwanted chemical reactions with the cathode surface and components of the electrochemical cell, such as electrolyte components other than the solid electrolyte. In some embodiments, the solid electrolyte layer (e.g., a LISICON layer) provides a chemical barrier layer that separates a first side of the electrochemical cell having a first electrolyte from a second side of the electrochemical cell having a second electrolyte different from the first electrolyte, and thus can provide a means for combining two separate electrolytes, each of which is particularly suitable for selected anode and cathode compositions.

[0228] Fig. 10E A schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein the conductive side of the separator proximate the anode reduces anode loss; for example, by preventing dendrite growth, reducing anode loss, such as in mossy deposits, during cycling and preventing the passage of cathode material to the anode, which interrupts electrical contact between the anode particles and the current collector and deteriorates the performance of the electrochemical cell. For example, the conductive side proximate the cathode increases the conductivity of the cathode, which can lead to longer life cycles, higher power and thicker cathodes and higher energy cathodes and thus better electrochemical cells. The electrochemical cell includes an anode, such as a lithium anode; a cathode, such as a LiFePO4, LiCoO2 cathode; a separator system including two high mechanical strength layers with complementary patterns of pores, three low ionic resistance layers, and a mechanically, chemically and thermally resistant ion conductive layer, such as a carbon black layer. Fig. 10C The overall electrochemical cell geometry in Fig. 10B , 10C and 10D, wherein a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode. However, in Fig. 10D In an electrochemical cell, the first high mechanical strength layer comprises a perforated metal layer and the second high mechanical strength layer comprises a perforated electrical insulating layer, such as a perforated Kapton layer. In this embodiment, the perforated metal layer and the perforated Kapton layer have complementary patterns of holes to prevent crystal growth. In addition, a mechanically, chemically and thermally resistant ionically conductive carbon black layer is disposed adjacent to the cathode and optionally in electrical and / or physical contact with the cathode.

[0229] Fig.10FA schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein a perforated separator sheet and a porous layer act as a separator by providing electrical insulation between electrodes, yet providing ionic connection between electrodes via a fluid electrolyte (aqueous or non-protic). The electrochemical cell includes an anode such as a silicon, Li, Zn, ZnO, graphite, or LTO anode; a cathode such as a LiFePO4, LiCoO2, sulfur, or Ag cathode; and a separator system including two high mechanical strength layers with complementary patterns of pores and three low ionic resistance layers. As shown Fig.10F As shown, a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode. However, in Fig.10F In the electrochemical cell, the first high mechanical strength layer and the second high mechanical strength layer independently comprise mechanically, chemically and thermally resistant electrically insulating layers, such as perforated metal layers having one or more insulating coatings, such as PE or PP coatings.

[0230] Figure 10G A schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein the shape memory effect of two high mechanical strength layers results in very good mechanical contact between the separator and the electrode. The electrochemical cell includes an anode such as a silicon, Li, Zn, ZnO, graphite or LTO anode; a cathode such as a LiFePO4, LiCoO2, sulfur or Ag cathode; and a separator system including two high mechanical strength layers with complementary patterns of pores and three low ionic resistance layers. Figure 10G The overall electrochemical cell geometry in Fig.10F The overall electrochemical cell geometry shown, wherein a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode. However, in Figure 10G In the electrochemical cell, the first high mechanical strength layer and the second high mechanical strength layer independently include mechanically, chemically and thermally resistant electrically insulating layers that exhibit shape memory effect, such as perforated Nitinol layers optionally coated with PE or PP.

[0231] Fig. 10HA schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein the superelasticity and / or shape memory effect of two high mechanical strength layers results in very good mechanical contact between the separator and the electrode. For example, in an embodiment of this aspect, an enhanced electrical contact is provided between the solid electrolyte and the cathode. The electrochemical cell includes an anode such as a silicon, Li, Zn, ZnO, graphite or LTO anode; a cathode such as a LiFePO4, LiCoO2, sulfur, Ag, carbon-air, carbon-water cathode; a separator system including two high mechanical strength layers with complementary patterns of pores, three low ionic resistance layers, and a solid electrolyte layer such as a LISICON or PEO (polyethylene oxide) layer. Fig. 10H The overall electrochemical cell geometry in Fig. 10B , 10C and the overall electrochemical cell geometry shown in 10D, wherein a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode, and wherein a solid electrolyte layer, such as a LISICON or PEO layer, is disposed between the third low ionic resistance layer and the cathode, so that ions can be transferred to the cathode surface. However, in Fig. 10H In an electrochemical cell of the invention, the high mechanical strength layer is a mechanically, chemically and thermally resistant electrically insulating layer with superelasticity or shape memory effect, such as a perforated Nitinol layer optionally coated with PE or PP. Fig. 10B As discussed above, the incorporation of a solid electrolyte layer (e.g., a LISICON or PEO layer) is useful for protecting the cathode, e.g., from unwanted chemical reactions with the cathode surface and components of the electrochemical cell, e.g., electrolyte components other than the solid electrolyte. In some embodiments, the solid electrolyte layer (e.g., a LISICON layer) provides a chemical barrier layer that separates a first side of the electrochemical cell having a first electrolyte from a second side of the electrochemical cell having a second electrolyte different from the first electrolyte, and thus can provide a means for combining two separate electrolytes, each of which is particularly suitable for selected anode and cathode compositions.

[0232] Fig.10IA schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein the superelasticity and / or shape memory effect of two high mechanical strength layers results in very good mechanical contact between the separator and the electrode. For example, in an embodiment of this aspect, an enhanced electrical contact is provided between the solid electrolyte and the cathode. The electrochemical cell includes an anode such as a silicon, Li, Zn, ZnO, graphite or LTO anode; a cathode such as a LiFePO4, LiCoO2, sulfur, Ag, carbon-air, carbon-water cathode; a separator system including two high mechanical strength layers with complementary patterns of pores, three low ionic resistance layers, and a solid electrolyte layer such as a LISICON or PEO layer. Fig.10I The overall electrochemical cell geometry in Fig. 10B , 10C and the overall electrochemical cell geometry shown in 10D, wherein a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode, and wherein a solid electrolyte layer, such as a LISICON layer, is disposed between the third low ionic resistance layer and the cathode, so that ions can be transferred to the cathode surface. However, in Fig.10I In an electrochemical cell of the invention, the high mechanical strength layer is a mechanically, chemically and thermally resistant electrically insulating layer that exhibits superelasticity and / or shape memory effect, such as a perforated shape memory polymer layer. Fig. 10B As discussed above, the incorporation of a solid electrolyte layer (e.g., a LISICON or PEO layer) is useful for protecting the cathode, e.g., from unwanted chemical reactions with the cathode surface and components of the electrochemical cell, e.g., electrolyte components other than the solid electrolyte. In some embodiments, the solid electrolyte layer (e.g., a LISICON or PEO layer) provides a chemical barrier layer that separates a first side of the electrochemical cell having a first electrolyte from a second side of the electrochemical cell having a second electrolyte different from the first electrolyte, and thus can provide a means for combining two separate electrolytes, each of which is particularly suitable for selected anode and cathode compositions.

[0233] Fig.10J A schematic diagram is provided of a cross-sectional view of an electrochemical cell having a separator, wherein the conductive side of the separator reduces anode loss, such as in large deformations of silicon, during cycling, which interrupts electrical contact between anode particles and current collectors and deteriorates the performance of the electrochemical cell. The electrochemical cell includes an anode, such as a silicon anode; a cathode, such as a LiFePO4 or LiCoO2 cathode; and a separator system including two high mechanical strength layers having complementary patterns of pores and three low ionic resistance layers. Fig.10J The overall electrochemical cell geometry in Fig.10F The overall electrochemical cell geometry shown, wherein a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, and a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the cathode. However, in Fig.10J In an electrochemical cell, the first high mechanical strength layer includes a mechanically, chemically and thermally resistant ion-conductive and electronic-conductive layer, such as a perforated metal layer, positioned close to the anode; and the second high mechanical strength layer includes a mechanically, chemically and thermally resistant non-conductive perforated layer, such as a perforated Kapton layer, positioned close to the cathode.

[0234] Figure 10K A schematic diagram of a cross-sectional view of an electrochemical cell having a separator is provided, wherein the conductive side of the separator near the anode during cycling reduces anode losses, such as in large deformations of the silicon, which interrupt electrical contact between the anode particles and the current collector and deteriorate the performance of the electrochemical cell. In embodiments of this aspect, the conductive side proximate the cathode increases the conductivity of the cathode, which can result in longer life cycles, higher power and thicker cathodes and higher energy cathodes and thus better electrochemical cells. The electrochemical cell includes an anode, such as a silicon anode; a cathode, such as a LiFePO4 or LiCoO2 cathode; and a separator system including three high mechanical strength layers and three low ionic resistance layers having complementary patterns of pores. As Figure 10K As shown, a first low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the anode and the first high mechanical strength layer, a second low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the first high mechanical strength layer and the second high mechanical strength layer, and a third low ionic resistance layer, such as a very porous layer (e.g., ≥ 80%), is disposed between the second high mechanical strength layer and the third high mechanical strength layer. Figure 10K In an electrochemical cell, the first high mechanical strength layer and the third high mechanical strength layer positioned close to the anode and the cathode, respectively, include mechanically, chemically and thermally resistant layers, such as perforated metal layers; and the second high mechanical strength layer arranged between the first high mechanical strength layer and the second high mechanical strength layer includes a mechanically, chemically and thermally resistant electrical insulating and ion conductive layer, such as a perforated Kapton layer.

[0235] Fig.10LA schematic diagram of a cross-sectional view of an electrochemical cell embodiment is provided that provides a hard, chemically resistant and / or heat resistant layer that is ionically and conductively positioned adjacent to a cathode. The electrochemical cell of this embodiment includes an anode, such as a silicon anode; a cathode, such as LiFePO4 or LiCoO2; a series of layers that include a pair of very porous layers, such as an 80% porous PE layer, an electronically and ionically conductive hard, chemically resistant and / or heat resistant layer such as carbon black, and an ionically conductive but electrically insulating hard, chemically resistant and / or heat resistant layer such as PE, PP or perforated Kapton. The use of a hard, chemically resistant and / or heat resistant layer that is ionically and electronically conductively positioned adjacent to a positive electrode allows the use of a cathode material that expands and contracts during charge / discharge, which can route electrons to a cathode current collector because the layer provides a second conductive path for current collection.

[0236] Figure 10M A schematic diagram providing a cross-sectional view of an electrochemical cell embodiment is provided. The electrochemical cell of this embodiment includes an anode, such as a silicon, Li, zinc, zinc oxide, LTO, graphite, Na, Mg, Sn, Cd, Pb, or PbO2 anode; a cathode, such as LiFePO4, LiCoO2, sulfur, FeS, V2O5, LVO, carbon-air, carbon-water, silver, silver oxide, Ni, Pb, PbO2, or carbon; an ionically conductive but electrically insulating hard, chemically resistant, and / or heat resistant separator layer, such as PE, PP, Kapton, or fibrous cellulose; and a pair of thin conductive coatings, such as a 5 nm carbon black layer, which are optionally disposed on the cathode surface, the anode surface, and / or the outer surface of the separator. The use of a thin conductive coating adjacent to one or both electrodes enables a second conduction path for current collection through the layer, which can route electrons to the cathode or anode current collector. The conductive layer on the outside of the electrode reduces the capacity loss such as in silicon, where large deformation during cycling can interrupt the electrical contact between the electrode active particles and the current collector and deteriorate the performance of the electrochemical cell. At the same time, the conductive coating (such as nano-thick carbon black) is ionically conductive and allows ions such as Li ions to pass easily.

[0237] Fig.10NA schematic diagram providing a cross-sectional view of an electrochemical cell embodiment is provided. The electrochemical cell of this embodiment includes an anode, such as lithium; one or more porous layers, such as 80% porous PE; a hard, chemically resistant and / or heat-resistant layer that is electronically conductive and ionically conductive, such as a perforated metal; a hard, chemically resistant and / or heat-resistant layer that is ionically conductive but electrically insulating, such as a perforated Kapton layer; a hard, chemically resistant and / or heat-resistant layer that is electronically conductive and ionically conductive, such as carbon black; and a cathode, such as LiFePO4 or LiCoO2. The conductive material adjacent to the anode reduces anode loss, such as by stopping dendrite growth, reducing anode loss such as in mossy deposits during cycling and preventing the passage of cathode material to the anode, which interrupts the electrical contact between the anode particles and the current collector, thereby deteriorating the performance of the electrochemical cell. The conductive material adjacent to the cathode increases the conductivity of the cathode, which can lead to longer life cycles, higher power and thicker cathodes and higher energy cathodes and thus better electrochemical cells.

[0238] Fig.10O A schematic diagram providing a cross-sectional view of an electrochemical cell embodiment is provided. The electrochemical cell of this embodiment includes an anode, such as silicon; one or more porous layers, such as 80% porous PE; at least one hard, chemically resistant and / or heat-resistant layer that is electronically conductive and ionically conductive, such as a perforated metal, which is positioned adjacent to the anode and cathode, optionally separated by a porous layer; an ionically conductive but electrically insulating hard, chemically resistant and / or heat-resistant layer, such as a perforated Kapton layer; and a cathode, such as LiFePO4 or LiCoO2. The conductive material adjacent to the anode reduces anode losses, such as in silicon, where large deformations during cycling interrupt electrical contact between the anode particles and the current collector and deteriorate the performance of the electrochemical cell. The conductive side adjacent to the cathode increases the conductivity of the cathode, which can lead to longer life cycles, higher power and thicker cathodes and higher energy cathodes and thus better electrochemical cells.

[0239] Figure 10PA schematic diagram providing a cross-sectional view of an electrochemical cell embodiment is provided. The electrochemical cell of this embodiment includes an anode, such as silicon; one or more porous layers, such as 80% porous PE; at least two hard, chemically resistant and / or heat-resistant layers that are electronically conductive and ionically conductive, such as carbon black; a hard, chemically resistant and / or heat-resistant layer that is ionically conductive but electrically insulating, such as a perforated Kapton layer; and a cathode, such as LiFePO4 or LiCoO2. The conductive material adjacent to the anode reduces anode losses, such as in silicon, where large deformations during cycling interrupt electrical contact between the anode particles and the current collector and deteriorate the performance of the electrochemical cell. The conductive side adjacent to the cathode increases the conductivity of the cathode, which can lead to longer life cycles, higher power and thicker cathodes and higher energy cathodes and thus better electrochemical cells.

[0240] Fig.11A and 11B The porous patterned layers of some separator systems of the present invention are provided, for example Figure 2-1 0. For example, in Fig.11A and 11B In the embodiments shown, there are alternating porous areas (schematically shown as dashed areas) and solid areas (schematically shown as filled areas). In these embodiments, layer R can provide the inverse pattern of holes of the design of layer F. Fig.11A and 11B In , the pattern features alternating rectangular porous and solid areas. Optionally, some of the pores in layers F or R are filled with a solid or gel electrolyte.

[0241] Example 2: High-performance, inexpensive rechargeable lithium batteries: Designing separators and electrodes The highest energy batteries known to date use metals such as zinc and lithium, which are inexpensive and have very high energy / power density. At the same time, recharging these batteries poses a major safety hazard. The requirement to mitigate safety issues is a very strong yet highly conductive separator that can resist dendrite formation, accidents, and thermal runaway.

[0242] Using engineering methods in constructing separators and electrodes, the separator system of the present embodiment provides significant improvements in safety, durability, power and energy performance in various battery chemistries. One method of the present invention is to apply engineering knowledge and methods to the most effective chemical structures used in the battery industry. As shown in the present embodiment, the present invention provides a manufacturing-friendly method to manufacture ultra-safe high-capacity separators. Button cell tests made of commercial lithium metal, LiFePO4 and current separator systems show separator conductivity comparable to conventional Celgard separators, mechanical strength of solids and an operating temperature range of -40 to 200 degrees Celsius. The separator system of the present embodiment can be an essential part of a Li-ion-based supercapacitor, a Li-ion-based flow battery, Li-sulfur, Li-air, Li-water, a Zn battery, a manganese battery, a silicon anode battery or a Zn-air battery.

[0243] The goal of certain aspects of the present invention is to improve the rechargeability, safety and cycle life of existing non-rechargeable high energy chemistries such as lithium metal and zinc batteries and silicon anode batteries and air cathode batteries and flow batteries, and to provide advanced electrochemical systems for high energy rechargeable metal-air batteries that provide economical solutions to energy storage challenges, especially in utility grade batteries.

[0244] The current state-of-the-art lithium metal batteries are not rechargeable, mainly due to dendrite formation that can cause internal short circuits and lead to fire and explosion. At the same time, silicon, as a potential high-energy anode, undergoes very large shape changes and loses its electrical contact with the current collector unless very expensive nano-organic silicon that is carefully grown in a preferred direction (non-scalable) is used. Many different electrolytes and additives have been tested and cannot be useful in industrial-grade systems. Recently, various solid electrolytes have been introduced to enhance safety, but they have electrical conductivity several orders of magnitude lower than liquid electrolyte-separator systems, and lose their performance after very few cycles due to fatigue, cracks, and lost electrode-electrolyte contact.

[0245] Using novel and scalable processes, aspects of the present invention provide highly porous separator systems (e.g., greater than or equal to 10 μm for liquid electrolytes at room temperature) with mechanically stiff materials that resist dendrite growth (e.g., elastic modulus greater than 1 GPa and temperature range of -200 to 400 degrees Celsius). -2S / cm conductivity). Embodiments of the current separator system provide new device structures for realizing high energy low cost utility-grade batteries for various chemical structures. Embodiments of the current separator system also provide accident-safe transportation batteries. Experimental results show that, for example, batteries integrating the current separator system can achieve more than 5,000 cycles with no capacity loss or minimal capacity loss. In addition, some separator systems can be easily implemented into casting and roll-to-roll processing methods that are already used in current lithium battery manufacturing.

[0246] An important feature of certain embodiments of the present invention is a multi-layer separator system that provides both high conductivity and high safety. Fig.12 A schematic diagram of a cross-sectional view of an electrochemical cell including a separator system of the present invention is provided. Fig.12 As shown, the electrochemical cell comprises an anode (3) and a cathode (4) separated from each other by a separator system (5). In this embodiment, the separator system (5) comprises a plurality of layers, including a perforated layer (1 and 1') comprising a solid material and having a pattern and framework of holes and / or a very porous layer (2). The high elastic modulus of the perforated layer of the separator material prevents dendrites from directly piercing the barrier. Fig.14 Examples of patterns of holes useful in the perforated layer of the separator system of the present invention are provided. Fig.14 As shown, the perforated layer of the separator system may have holes with a circular or rectangular shape. Fig.14 Complementary patterns of perforated layers useful for preventing dendrite growth, short circuits, and mechanical failures are also shown. For example, panels A and B provide complementary patterns of holes that do not overlap when set in an offset alignment of certain separator systems. Panel C provides a schematic diagram showing the superposition of the patterns in panels A and B, indicating that the offset alignment results in no overlap of holes. Similarly, panels F and G provide complementary patterns of holes that do not overlap when set in an offset alignment of certain separator systems. Similarly, panels H and I provide complementary patterns of holes that do not overlap when set in an offset alignment of certain separator systems. Similarly, panels J and K provide complementary patterns of holes that do not overlap when set in an offset alignment of certain separator systems. Similarly, panels L and M provide complementary patterns of rectangular holes that do not overlap when set in an offset alignment of certain separator systems.

[0247] The large number of holes in the perforated layer ensures high conductivity of the separator, and the offset alignment of the holes in the continuous layer ensures that there is no direct path between the electrodes. The force from the high mechanical strength layer on the dendrites slows down or stops the dendrite growth. In an electrochemical cell, this significantly improves the performance of the cell. Fig.13 A schematic diagram is provided for simplicity to illustrate the desired trajectory of dendrite growth in the electrochemical system of the present invention. In this figure, the dendrite is shown as a curved line extending from the anode to the cathode. Fig.13As shown, the dendrite will have to make several bends to pass through the perforated layer and create a short circuit. From a strictly mechanical point of view, the elastic modulus of lithium (5 GPa) is too high to allow continuous bending of dendrites over small lengths (less than 0.1 mm); the energy required to bend a straight strand is dx, where E is the elastic modulus, l is the moment of inertia, and R(x) is the radius of curvature at each point, and finally, L is the length of the element. From a chemical engineering point of view, dendrites have too much motion frustration to overcome such a spiral growth path. In addition, the resistive pressure of the solid component of the high mechanical strength layer slows down the growth of dendrites and can even prevent the growth of dendrites. A layered separator system including a perforated layer with a complementary pattern of holes effectively prevents dendrite growth and thus prevents short circuits. The materials and manufacturing methods necessary for such a composite separator system are compatible with the current battery manufacturing infrastructure, allowing low-cost implementation for current battery manufacturing. The present invention provides a cost-effective, safe and high-energy lithium battery with very slow charging (e.g., C / 10) and very fast discharge (e.g., 4C) that is very suitable for load balancing in the power grid. The present invention also provides a process for manufacturing a layered separator, resulting in an industrial-friendly battery characterized by the conductivity of a liquid electrolyte, the safety of a solid electrolyte, a high cycle life and low cost. Optionally, in certain embodiments, this is achieved by a layer made of a shape memory material such as Nitinol or a shape memory polymer. When the layer is placed in a battery, applying a pre-stress such as an in-plane tension on the shape memory layer of the separator will induce an out-of-plane pressure on the electrode. This can be particularly useful in larger batteries such as 18650 cylindrical batteries or wound batteries.

[0248] The electrochemical system of the present invention is also compatible with the use of engineered electrodes, such as pre-stressed electrodes. Lithium metal performs significantly better when compressed in the out-of-plane direction by equalizing its surface (less moss and less dendrites). In addition, out-of-plane compression in silicon anodes leads to much better contact with the current collector and much higher life cycle. This aspect of the present invention can also be helpful in solid-state batteries by maintaining good contact between the electrode and the solid electrolyte and increasing cycle life and performance. Optionally, in some embodiments, this is achieved by a layer made of shape memory material such as nitinol or shape memory polymer. When the layer is placed in the battery, applying a pre-stress such as in-plane tension on the shape memory layer of the separator will cause out-of-plane pressure on the electrode. This can be particularly useful in larger batteries such as 18650 cylindrical batteries or wound batteries.

[0249] To further demonstrate the beneficial attributes of the present invention, more than 100 button cells incorporating a composite layer separator system were manufactured and evaluated. Some of the separators tested were currently 0.125 mm thick and maintained 75% capacity at C / 2 compared to 0.025 mm Celgard. Safety testing including high current cycling, 55 mA / cm2 for 300 cycles, demonstrated that the separator system was robust and the battery was not shorted internally. In addition, there was no measurable degradation or capacity loss after hundreds of cycles, in contrast to the 5-layer Celgard separator (0.125 mm thick) that was completely destroyed. The present invention includes separator systems that optionally have a total thickness of 0.075 mm. The present invention optionally includes a 0.025 mm thick roller of a separator system useful for a 10 kWh cylindrical 18650 lithium metal battery pack with 400 Wh / kg energy and 5000 cycles.

[0250] Grid-level energy storage is currently dominated by pumped hydroelectric power plants, with over 99% of current storage possible only in very few limited locations and applications, unsuitable for society's growing storage needs. Other solutions have significant disadvantages. Compressed air technology suffers from very low round-trip efficiencies of less than 20%. Electrolyte capacitors and flywheels have very low energy / cost ratios. Flow batteries, which serve as a combination of high power and high energy, are very complex and expensive. Current batteries also suffer from high cost / energy and cost / power ratios (approximately ). The latest high energy lithium-metal, lithium-air and nano-silicon chemistries have major safety / cost issues as mentioned earlier.

[0251] In some embodiments, the separator-electrode design of the present invention enables various rechargeable high-energy chemistries that are currently not considered safe and / or have short cycle life. Using industrial manufacturing methods (e.g., CNC, molding, casting), the present invention combines electrochemistry with engineering to address safety issues in the latest battery technology. The current separator system combined with the high-energy electrode provides safe, long cycle life high-energy batteries for grid storage and also electric vehicles on an industrial scale.

[0252] The current system and method are scalable and industrial friendly. Enhanced separator performance can be achieved via several approaches that are amenable to the current system and method. Improving conductivity by making smaller holes (0.010 to 0.100 mm) and using thinner layers (0.005 mm) is a useful approach for obtaining high performance systems. In addition, maintaining the desired offset alignment and connecting layers by heating at the boundaries and other selected areas can be used to obtain a separator system that provides enhanced security.

[0253] Fig.15A graph of the charge and discharge capacity (mAh / g) of an electrochemical cell as a function of the number of cycles is provided, the electrochemical cell having: (A) a multilayer separator system of the present invention having a total thickness of 125 microns, and (B) a Celgard separator having a thickness of 25 microns. The evaluated CR2032 button cell was made of a Li foil 0.5 mm thick anode, a LiFePO4 (0.0142 g) cathode, 1M LiPF6 in EC:DEC:DMC (1:1:1). The voltage limits were 3 v (discharge) and 4 v (charge). The formation, 3 cycles at C / 5 and C / 2 cycles were distinguished from a sharp drop in capacity. The top line shows a separator fabricated with two perforated Kapton layers as mechanically strong layers and 3 perforated Celgard 2325 layers as low resistance layers. The bottom line shows a separator fabricated with two perforated Kapton layers as mechanically strong layers and 3 perforated Celgard 2325 layers as low resistance layers. The cells were tested at room temperature and no measurable capacity drop was observed after 40-50 cycles. Fig.15 The experimental results presented indicate that the current separators offer low electrical resistance and are therefore compatible with a variety of electrochemical systems.

[0254] Fig.16 A graph of the charge and discharge capacity (mAh / g) of an electrochemical cell (A) having a multilayer separator system of the present invention, a lithium metal anode and a LiCoO2 cathode as a function of the number of cycles is provided in comparison with an electrochemical cell (B) having a conventional separator. The electrochemical cell was a button cell and was evaluated at a discharge rate of C / 2. The evaluated CR2032 button cell was made of a 0.5 mm thick Li foil anode, a 0.1 mm thick LiCoO2 cathode, and 1M LiPF6 in EC:DEC:DMC (1:1:1). The voltage limits were 3 v (discharge) and 4.2 v (charge). The formation, 5 cycles at C / 24 and C / 2 cycles were distinguished from a sharp drop in capacity. The red lines (indicated by the letter B) 1, 5, 6 show cells manufactured with separators, which were manufactured with two perforated Kapton layers (2 mm diameter holes) as mechanically strong layers and 3 Celgard 2325 layers as low resistance layers. The blue line (indicated by the letter A) 2, 3 shows a reference electrode fabricated with perforated Kapton between two Celgard layers. The battery was tested at room temperature. The battery was cycled at C / 2, and then cycled at C / 24 for several cycles, and then cycled at C / 2 again. The experimental results indicate that the capacity loss is not due to any chemical reaction in the battery, and is likely due to the resistance of the perforated Kapton layer in the electrochemical cell being evaluated. Fig.16 It is shown that the use of other materials, surface treatments or a uniform distribution of pores and thus smaller pores is necessary to achieve good capacity in the cell under some experimental conditions.

[0255] Fig.17 A graph of the charge and discharge capacity (mAh / g) of an electrochemical cell (i) having a multilayer separator system of the present invention, a lithium metal anode and a LiFePO4 cathode as a function of the number of cycles is provided, compared to an electrochemical cell (ii) with 3 conventional separators having a thickness of 75 microns and a Celgard separator (iii) having a thickness of 25 microns. The electrochemical cell was a button cell and was evaluated at a discharge rate of C / 2. The evaluated CR2032 button cell was made of a Li foil 0.5 mm thick anode, a LiFePO4 0.1 mm thick cathode, and 1M LiPF6 in EC:DEC:DMC (1:1:1). The voltage limits were 3 v (discharge) and 4 v (charge). The formation, 5 cycles at C / 24 and C / 2 cycles were distinguishable from a sharp drop in capacity. Lines I, H show cells made with a single Celgard layer. Lines A, B, C show cells with separators made with two perforated Kapton layers as mechanically strong layers and 3 Celgard 2325 layers as low resistance layers. Lines F and D show reference electrodes made with perforated Kapton between two Celgard layers. The cells were tested at room temperature. The tests demonstrated the importance of having a thin separator to achieve high capacity in the cell.

[0256] Fig.18 A schematic diagram showing an electrochemical cell of the present invention having a multilayer separator including three high mechanical strength layers having complementary patterns of pores, an anode, and a cathode is provided. Fig.19 Provides a diagram showing the Fig.18 The Li of the multilayer separator shown + Schematic diagram of the ion trajectory. Although Li + Ions can efficiently pass through Fig.19 The multilayer separator shown, however, dendrites cannot follow the same trajectory and are therefore prevented in certain embodiments of the invention. In addition, the forces from the high mechanical strength layer slow down or even prevent dendrite growth.

[0257] Fig. 20A graph of cell voltage (V vs. Li) versus cycle time (h) of electrostatic lithium peeled from two symmetrical (5 / 9)" lithium chips with the multilayer separator of the present invention is provided. In a CR2032 cell, a layer of the novel separator (0.125 mm thick) was fabricated with 2 Kapton layers as high strength layers and 3 Celgard layers next to them as low resistance layers. Celgard 2325 was used. The cell was prepared with 0.75 mm Li foil as electrode and 1M LiPF6 from Novolte in EC:DEC:DMC (1:1:1) as electrolyte. The Kapton holes were each 1 mm in diameter. The cells were tested in an argon filled dry box (H2O <0.1 ppm) at room temperature. The graph shows that the multilayer separator can safely block dendrite shorting and prevent catastrophic failure even at very high currents.

[0258] Fig. 22 Show Fig.15 The current [amperes] versus time [s] (top curve) and the voltage [v] versus time [s] (bottom curve) of the experiment. This is shown as the top red line.

[0259] Figure 23-28 Provided are photographs of perforated layers useful in separator systems of some embodiments. Fig.23 For example, pictures of different separator materials (5-Celgard separator: A) and new separators B)-D) after cycling at high current for several days are provided: A) 5-Celgard separator (from top left to bottom right: Li+Celgard, Li+Celgard, stainless steel current collector; Typical separator (Celgard) pierced and destroyed by lithium dendrites. As can be seen, the separator is no longer recognizable; B) Celgard layer between two perforated Kapton layers; C) Celgard in contact with the lithium electrode; D) Perforated Kapton. Lithium dendrites cannot penetrate the new separator. The Kapton layer of the new separator shown here is intact, although the Celgard on the right side of the Kapton layer is destroyed. For example, Figure 25-28 is a picture of a 1 mil Kapton film produced by laser cutting for use in the separator system of the present invention.

[0260] Fig.23Shown is a layer of a novel separator (0.125 mm thick) fabricated with 2 Kapton layers as high strength layers and 3 Celgard layers next to them as low resistance layers compared to 5 Celgard layers (0.125 mm thick) as a reference separator of a fabricated cell with ½" diameter in a case. Celgard 2325 was used. The cell was fabricated with 0.75 mm Li foil as electrode and 1 M LiPF6 from Novolte in EC:DEC:DMC (1:1:1) as electrolyte. The Kapton holes were each 2 mm in diameter. The cells were tested at room temperature and in an argon filled dry box (H2O <0.5 ppm) at 55 mA cycled for 45 minutes charge-discharge cycle: (A) Reference separator: shows 5-Celgard Reference separator: the battery is shorted; (B-D) shows parts of the new separator. The battery is not shorted. (B) New separator: the Celgard layer between the two perforated Kapton layers is intact; (C) New separator: the Celgard in contact with the lithium electrode shows severe damage; (D) New separator: the perforated Kapton is intact and maintains its structural integrity, preventing any short circuit. This figure shows that the multilayer separator can safely prevent dendrite shorting and prevent catastrophic failure even at very high currents. Fig.24 (Zoom in) and Fig.23 (zoomed out) The top and bottom diagrams show two adjacent layers in each design. Figure 25-28 Shown are several examples of solid layer designs made of Kapton. Laser cutting is used to make the holes. The size of each layer is ½ inch. The holes are either 1mm diameter or 2mm diameter.

[0261] Example 3: Lithium battery with multilayer separator system This example provides a description of an example of a lithium battery including the multilayer separator system of the present invention.

[0262] Example A: In this example, two layers of Kapton membrane (25 microns thick each) were used for the separator system. Each layer was perforated with Cartesian (vertical-horizontal) periodic holes, each hole was 1 mm in diameter, and there was a 1 mm distance between the walls. A 25 micron Celgard layer was placed between the two Kapton layers. A 25 micron Celgard layer was placed between each Kapton layer and the adjacent electrode. The electrodes were LiCoO2 and lithium metal films. The electrolyte was LiPF6 in a combination of EC-DMC-PC-DME.

[0263] Example B: In this example, two layers of Kapton membrane (25 microns thick each) were used for the separator system. Each layer was perforated with Cartesian (vertical-horizontal) periodic holes for the separator system, each hole was 1 mm in diameter, and there was a 1 mm distance between the walls. A 25 micron Celgard layer was placed between the two Kapton layers. A 25 micron Celgard layer was placed between each Kapton layer and the adjacent electrode. The electrodes were LiFePO4 and lithium metal film. The electrolyte was LiPF6 in a combination of EC-DMC-PC-DME.

[0264] Example C: In this example, two layers of Kapton membrane (25 microns thick each) are used for the separator system. Each layer is perforated with Cartesian (vertical-horizontal) periodic holes for the separator system, each hole is 1 mm in diameter, and there is a 1 mm distance between the walls. A 25 micron thick perforated Celgard layer with 3 holes (1 / 8 inch each) is placed between the two Kapton layers. A 25 micron thick perforated Celgard layer with 3 holes (1 / 8 inch each) is placed between each Kapton layer and the adjacent electrode. The electrodes are LiFePO4 and lithium metal film. The electrolyte is LiPF6 in a combination of EC-DMC-PC-DME.

[0265] Example D: In this example, two layers of PP membrane (each 25 microns thick and 3 / 4 inch diameter) were used for the separator system. Each layer was perforated with Cartesian (vertical-horizontal) periodic holes, each hole was 1 mm in diameter, and there was a 1 mm distance between the walls. A 25 micron thick Celgard ring was placed between the two PP layers. A 25 micron thick Celgard ring with an outer diameter of 3 / 4 inch and an inner diameter of 1 / 2 inch was placed between each PP layer and the adjacent electrode. The electrodes were LiFePO4 and lithium metal film. The electrolyte was LiPF6 in a combination of EC-DMC-PC-DME.

[0266] Example E: In this example, two layers of hard polyester film (each 5 microns thick and 3 / 4 inch diameter) are used for the separator system. Each layer is perforated with Cartesian (vertical-horizontal) periodic holes, each hole is 1 mm in diameter, and there is a 1 mm distance between the walls. A ring of microporous PE / PP / PE 5 microns thick is placed between the two hard polyester layers. A ring of microporous PE / PP / PE 5 microns thick and 3 / 4 inch outer diameter and 1 / 2 inch inner diameter is placed between each hard polyester layer and the adjacent electrode. The electrodes are LiFePO4 and lithium metal film. The electrolyte is LiPF6 in a combination of EC-DMC-PC-DME.

[0267] Example F: In this example, two stainless steel layers (5 micrometers thick each) are used. The steel layers are coated with a very thin electrically insulating layer (here 1 micrometer thick Teflon. Kapton or PVDF or PEO or PP or PE coatings can also be used). Each layer is perforated with Cartesian (vertical-horizontal) periodic holes, each hole is 0.5 mm in diameter and has a distance of 0.5 mm between the walls. A 5 micrometer microporous PE / PP / PE layer is placed between the two stainless steel layers. A 5 micrometer microporous PE / PP / PE layer is placed between each stainless steel layer and the adjacent electrode. The electrodes are LiFePO4 and lithium metal film. The electrolyte is LiPF6 in a combination of EC-DMC-PC-DME.

[0268] Example G: In this example, two layers of Kapton membrane (each 5 microns thick and 3 / 4 inch diameter) are used for the separator system. Each layer is perforated with Cartesian (vertical-horizontal) periodic holes, each hole is 1 mm in diameter, and there is a 1 mm distance between the walls. A 5 micron thick Celgard ring is placed between the two Kapton layers. A 5 micron thick Celgard ring with an outer diameter of 3 / 4 inch and an inner diameter of 1 / 2 inch is placed between the Kapton layer and the Li electrode next to the lithium metal film anode. A 25 micron thick and 3 / 4 inch diameter LISICON layer is placed between the second Kapton and the air carbon-cathode. The electrolyte on the Li side of the LISICON is LiClO4 in a combination of EC-DMC-PC-DME. The electrolyte on the air cathode side of the LISICON is an aqueous electrolyte.

[0269] Example H: In this example, two layers of PE membrane (each 5 microns thick and 3 / 4 inch diameter) are used for the separator system. Each layer is perforated with Cartesian (vertical-horizontal) periodic holes, each hole is 0.1 mm in diameter, and there is a 0.1 mm distance between the walls. A 25 micron thick and 3 / 4 inch diameter LISICON layer is placed between the second PE and the air carbon-cathode. The electrolyte on the Li side of the LISICON is LiPF6 in a combination of EC-DMC-PC-DME. The electrolyte on the air cathode side of the LISICON is an aqueous electrolyte.

[0270] Example I: In this example, two stainless steel layers (5 microns thick each) are used. The steel layer is coated with a very thin electrically insulating layer (here 1 micron thick Teflon) on the inner surface (the side facing the closer electrode). Each layer is perforated with Cartesian (vertical-horizontal) periodic holes, each hole is 0.1 mm in diameter and has a 0.1 mm distance between the walls. A 5 micron Celgard layer is placed between the two stainless steel layers. A 5 micron Celgard layer is placed between each stainless steel layer and the adjacent electrode. The electrodes are partially lithiated Si and partially lithiated sulfur. Batteries with this separator are expected to show higher cycle life and charge-discharge (power) rates.

[0271] Example J: In this example, two stainless steel layers (5 microns thick each) were used. The steel layer was coated with a very thin electrically insulating layer of 1 micron thick Teflon on the inner surface (the side opposite the closer electrode) and 1 micron thick polyethylene glycol on the outer surface (the side facing the closer electrode). Each layer was perforated with Cartesian (vertical-horizontal) periodic holes, each hole was 0.1 mm in diameter and had a 0.1 mm distance between the walls. A 5 micron cellulose separator layer was placed between the two stainless steel layers. A 5 micron cellulose separator layer was placed between each stainless steel layer and the adjacent electrode. The electrodes were Li metal and sulfur. The polyethylene glycol coating is expected to increase the cycle life of the battery.

[0272] Example K: In this example, two layers of polyimide membrane (each 5 microns thick and 3 / 4 inch diameter) are used for the separator system. Each layer is perforated with Cartesian (vertical-horizontal) periodic holes, each hole is 0.1 mm in diameter, and there is a 0.1 mm distance between the walls. A ring of 5 microns thick microporous PE / PP / PE is placed between the two polyimide layers. A ring of 5 microns thick microporous PE / PP / PE with an outer diameter of 3 / 4 inch and an inner diameter of 1 / 2 inch is placed between each polyimide layer and the adjacent electrode. The electrodes are a zinc anode and a carbon-based air cathode. The electrolyte is aqueous 6M NaOH.

[0273] Example L: In this example, two layers of hard PP film (5 microns thick and 3 / 4 inch diameter each) were used for the separator system. Each layer was perforated with Cartesian (vertical-horizontal) periodic holes, each hole was 0.1 mm in diameter. The electrodes were a zinc anode and a carbon-based air cathode. The electrolyte was aqueous 6M KOH.

[0274] Example M: ​​In this example, two layers of alumina membranes (each 5 microns thick and 3 / 4 inch diameter) are used for a separator system. Each layer is perforated with a random pattern of holes, each hole is 40% porous and gives less than 5% overlap of the hole pattern when placed on top of each other hole, each hole is 0.1 mm in diameter and has a 0.1 mm distance between the walls. A ring of microporous polyester 5 microns thick is placed between the two alumina layers. A ring of microporous polyester 5 microns thick and 3 / 4 inch outer diameter and 1 / 2 inch inner diameter is placed between each alumina layer and the adjacent electrode. The electrodes are a zinc anode and a carbon based air cathode. The electrolyte is aqueous 6M KOH.

[0275] Example N: In this example, two layers of hard polyester film (each 25 microns thick and 3 / 4 inch diameter) are used for a separator system. Each layer is perforated with a random pattern of holes, each hole is 40% porous and gives less than 5% overlap of the hole pattern when placed on top of each other hole, each hole is 1 mm in diameter and has a 1 mm distance between the walls. A ring of microporous polyester 25 microns thick is placed between the two hard polyester layers. A ring of microporous polyester 25 microns thick and 3 / 4 inch outer diameter and 1 / 2 inch inner diameter is placed between each hard polyester layer and the adjacent electrode. The electrodes are LiFePO4 and silicon membrane. The electrolyte is an ionic liquid.

[0276] Example O: In this example, two layers of Kapton membrane (each 5 microns thick and 3 / 4 inch diameter) coated with polyethylene glycol are used for the separator system. Each layer is perforated with Cartesian (vertical-horizontal) periodic holes, each hole is 0.01 mm in diameter, and there is a 0.01 mm distance between the walls. A 5 micron thick Celgard ring is placed between the two Kapton layers. A 5 micron thick Celgard ring with an outer diameter of 3 / 4 inch and an inner diameter of 1 / 2 inch is placed between each Kapton layer and the adjacent electrode. The electrodes are sulfur and lithium metal films. The electrolyte is a polymer electrolyte.

[0277] Example P: In this example, two layers of PP membrane (each 5 microns thick and 3 / 4 inch diameter) were used for the separator system. Each layer was perforated with Cartesian (vertical-horizontal) periodic holes, each hole was 0.001 mm in diameter, and there was a 0.001 mm distance between the walls. A ring of 5 microns thick microporous polyester was placed between the two PP layers. A ring of 5 microns thick microporous polyester with an outer diameter of 3 / 4 inch and an inner diameter of 1 / 2 inch was placed between each PP layer and the adjacent electrode. The electrodes were NMC and carbon membrane. The electrolyte was PEO.

[0278] Embodiment Q: Same as any of the above embodiments when the layers are connected to each other by PEO and PvDF at certain areas, such as the outside of each side.

[0279] Example R corresponds to Example G when the LISICON is 5 microns and is deposited on a hard layer on the air cathode side of a lithium-air cell.

[0280] In another embodiment, the porous patterned layer has the following physical dimensions, composition, and mechanical properties: ●Thickness: 125 microns, 75 microns, 50 microns or 25 microns.

[0281] ● Tensile strength: 150 MPa isotropic (Celgard: 15 MPa TD; 150 MPa MD) ● Porosity: 45% ● Elastic modulus: 2GPa ● Yield strength: 50 MPa ● Density: ~1.3 g / cm 3 ● MIT folding endurance: 10,000 cycles ● Elmendorf tear strength: 0.1N ● Graves tear strength: 15N ● Impact strength: 50 N.cm ● Shrinkage rate at 150 degrees Celsius for 30 minutes: 0.2 (Celgard: 5-10%) ● Dielectric strength ASTM D-149-91: 250 V / m ● Dielectric constant: 3.5 ● Thermal expansion coefficient: 20 ppm / degree Celsius.

[0282] Electrochemical cells including multilayer separators with porous patterned layers having these properties exhibit useful performance characteristics. When half-cells [button cells]: LiFePO4|LP71|Li were tested, for example, after 200 cycles: at C / 5, the capacity was ~140 mAh / g; at C / 2, ~120 mAh / g. Force deflection testing using external pressure showed that the cell did not short but ceased to function. Analysis of the separator system after 300 cycles at C / 2 showed little or no degradation, and the separator system was able to be used in another cell.

[0283] Tables 1 and 2 provide a summary of the physical dimensions and properties of the high mechanical strength layer and separator systems of certain embodiments of the present invention.

[0284] Table 1: Physical dimensions and properties of the high mechanical strength layer

[0285] Table 2: Physical dimensions and characteristics of the divider system

[0286] The resistivity of the separators in Table 2 was measured in 1 M LiPF6 EC:EMC (30:70 by volume). For electrochemical evaluation, a ½" coin cell electrochemical cell with Al-Al electrodes was used to characterize the separators. The separators were fabricated as celgard / perforated kapton / celgard / perforated kapton / celgard, each 25 μm thick.

[0287] Example 4: Separator comprising a thermally conductive layer such as a coated metal mesh In some aspects, the separator system of the present invention includes one or more porous patterned layers, which are coated metal layers, such as metal mesh with an outer insulating coating, such as Al coated with PP or Al coated with alumina or thermally conductive ceramics such as Al2O3. The embodiments of this aspect are beneficial for significantly increasing the life of the battery. In an embodiment, for example, the metal mesh (Al, nickel, copper, stainless steel) has a very high mechanical strength over a very wide temperature range; the metal separator is a thermally conductive material that makes the temperature of the battery uniform and significantly improves the safety and life of the battery. In an embodiment, the microporous layer of the separator is a PTFE-coated (or PP-coated or PEO-coated or Al2O3-coated or PET-coated or PVDF-coated) aluminum mesh layer (e.g., Al mesh, 40% opening: 3 layers, 5 microns per layer, or 2 layers, 1 / 3 mil per layer; in one embodiment, the Al layer is coated with PTFE, for example 2 microns thick on each side. In another embodiment, only the Al layer close to the anode is coated. In another embodiment, the Al layer is coated and the side is arranged to contact the electrode.

[0288] Example 5: New method for producing thin films: web- or fiber-supported ceramic products and their use as membranes, for example as solid electrolytes in electrochemical cells such as Li-air batteries or as filters in the bio-industry or food industry or in filtration Background: Li-air and Li-sulfur batteries have energy densities that are orders of magnitude higher than current batteries. One method of preparing these batteries is to use a semi-permeable membrane such as LISICON, which allows ion transport but prevents any other material from passing through, to protect the anode from contamination by the cathode material or its impurities. Thick solid electrolyte membranes not only show higher ionic resistance and cause energy loss and power loss, but also form cracks and losses related to the electrode in several cycles. In particular, it is well known in solid mechanics that there is a critical thickness that is thinner than the critical thickness of plastic deformation and cracks can be avoided. Therefore, in order to have high energy efficiency, high power density, fast charging and high cycle life, the protective film should be as thin as possible. Today, the preparation of ceramics such as LISICON membranes that are 50 microns thick or less is a major challenge; more often, pinholes are formed during the preparation of thin ceramics and therefore small particles can pass through the holes, and the ceramic loses its function as a semi-permeable membrane. This embodiment proposes a new method for preparing thin (less than 50 microns) and very thin (less than 5 microns) solid electrolytes, especially ceramic-based solid electrolytes. The applications are widespread and in many industries; such as, for example, ceramic membranes as solid electrolytes in electrochemical cells and as filters in the pharmaceutical industry or the biotechnology industry or in food processing.

[0289] In certain embodiments, the membrane is a composite solid electrolyte / mesh system or a composite solid electrolyte / fiber system, wherein the toughness of the mesh or fibers prevents cracks and pinholes in the ceramic during fabrication of the membrane and during operation of the membrane.

[0290] The mesh is optionally in a periodic form, occupying only a small portion of the ceramic system supported by the total mesh. For example, the mesh volume may be only 5-15% of the volume of the ceramic portion. In addition, the mesh is optionally completely inside the ceramic portion, or is optionally exposed on one or both sides of the ceramic.

[0291] The mesh or fiber material preferably has excellent ductility and strength such as made of metal or alloy (such as stainless steel, aluminum, copper or alloys thereof). The mesh is optionally made of polymers such as PE, PP, Kapton, PVDF, PVC or PMMA. The mesh is optionally made of glassy materials such as aluminum oxide or silicon dioxide or titanium dioxide.

[0292] The solid electrolyte is optionally any solid electrolyte such as LISICON or NASICON or PEO.The solid electrolyte is optionally used in an electrochemical cell such as a battery or an electrolytic capacitor or a fuel cell or a flow battery.

[0293] Because it is difficult to make thin solid electrolytes due to the difficulty in making thin ceramic layers, a system of solid electrolytes supported by a mesh or fiber is useful. For example, the difficulty may be due to the formation of cracks during the manufacturing process, such as the generation of pinholes in thin LISICON used for lithium battery applications such as Li-air batteries. The mesh or fiber supported system relieves stress inside the ceramic, such as a solid electrolyte such as LISICON, and thereby prevents cracks and holes such as pinholes during the preparation of the ceramic. In certain embodiments, it also helps to relieve stress caused by cycling and this improves cycle life.

[0294] Since the manufacture of thin films is difficult due to the difficulty in manufacturing thin layers of ceramic, a system of mesh or fiber supported membranes is useful. For example, the difficulty may be due to the formation of cracks during the manufacturing process, such as the creation of pinholes in a film used for filter applications such as in the bio-industry or in the food industry or in liquid filtration. A mesh or fiber supported system relieves stress inside the ceramic and thereby prevents cracks and holes such as pinholes during the preparation of the ceramic.

[0295] Other applications include fuel cell membranes or electrolyte capacitors or flow batteries or semisolid batteries or cathode redox flow batteries or solvated electrode batteries.

[0296] The method described in this example results in a mechanically strong matrix wherein the web / fibers are mechanically tough, resulting in a strong and tough overall performance of the system. This has been understood in the overall performance of systems such as the martensite / austenite system; TRIP and maraging steels, more recently in metallic glasses and in reinforced concrete, but has never been applied to formation processes and especially not to the formation of films or thin ceramics (which, if applied, usually and often suffer from pinholes and cracks during manufacturing).

[0297] Fig.29 Examples showing the application of supported membranes in electrochemical cells. Fig.29 In the embodiment, an anode 3101 (e.g., lithium) is positioned adjacent to an anode organic electrolyte 3102 (e.g., LiClO4 in PC-EC) and a separator (e.g., Celgard), and a membrane 3103 (e.g., comprising a LISICON solid electrolyte) separates the anode electrolyte 3102 from a porous cathode (e.g., a sulfur or air cathode) and a cathode electrolyte (e.g., an aqueous electrolyte) 3104. Current collectors 3105 and 3106 are positioned in contact with the anode 3101 and the porous cathode / catholyte 3102.

[0298] Fig.30 Some possible configurations of the film are shown, such as Fig.30Here, the ceramic 3207 is supported by a mesh and / or fibers 3208.

[0299] Example 6: Active membrane: Conductivity-assisted membrane and its use as an active separator in an electrochemical cell such as a battery Previously membranes and especially separators in electrochemical cells were only passive components. Typically, separators in electrochemical cells are non-conductive components that electrically separate two opposing electrodes. This embodiment describes an active membrane, in particular as a separator in an electrochemical cell, such as a battery.

[0300] For example, a multilayer film includes two or more layers such that at least one of the layers at either end of the film is conductive; and at least one of the intermediate layers is non-conductive such that there is no electrical connection between the two exterior faces of the film.

[0301] Optionally, some of the layers are deposited or coated on each other. Such a film is optionally used as a separator in an electrochemical cell. Optionally, some of the layers are deposited or coated on another layer or on either of the electrodes. Optionally, the outer conductive layer causes a new electron path for the outer particles of the adjacent electrode and thereby increases the electronic conductivity of the adjacent electrode material.

[0302] Optionally, the separator of this embodiment is used in an electrochemical cell, such as where the electrode material undergoes shape changes due to charge-discharge, which can result in at least partial loss of electronic conductivity between the electrode material and a corresponding current collector.

[0303] Electrochemical cells useful for the described separators include, but are not limited to, lithium batteries. Lithium batteries optionally include a separator and an optional silicon anode. Optionally, the cathode is lithium oxide or sulfur or carbon or air. Electrochemical cells useful for the described separators also include alkaline batteries and metal-air batteries.

[0304] Optionally, in a multilayer film, such as described above, each of the conductive layers is a porous layer or a perforated layer or a mesh made of a metal such as stainless steel or aluminum or copper or Ni or tin. Optionally, the metal layer is between the electrode and the non-conductive layer of the membrane. Optionally, the non-conductive layer is a coating on one side of the metal layer, for example a polymer such as PTFE or PVDF or PEO or PMMA or PE or PP or PET or Al2O3.

[0305] Useful films include films wherein the total thickness of the film is less than 500 microns. Useful films include films wherein the total thickness of the film is less than 100 microns or less than 50 microns. Optionally, the total thickness of the film is less than 25 microns or less than 5 microns.

[0306] Optionally, the separator or membrane described in this embodiment has an ionic resistance of less than 10 Ω cm2 or less than 1 Ωcm 2 Optionally, the separator or membrane described in this embodiment has a porosity of at least 30% or at least 70%. Optionally, the outer conductive layer of the separator or membrane described in this embodiment causes a change in the electric field at least near the corresponding electrode, for example when compared to a separator or membrane lacking an outer conductive layer. In some cases, the electric field modification due to the conductive layer of the separator results in more uniform lithium deposition during charging, and thereby increases the performance, life cycle and efficiency of the electrochemical cell.

[0307] Optionally, the membrane of this embodiment is useful in electrodeposition such as electrodeposition of metals such as gold, silver or lithium or zinc or copper or alloys. Optionally, the membrane of this embodiment is useful as a separator in an electrochemical cell such as a rechargeable lithium metal cell.

[0308] Figures 31A-31D Embodiments of using the membrane as a separator in an electrochemical cell, such as a battery, are described. Figures 31A-31D , the current collectors are identified as elements 3301A and 3301B; the active electrode particles (e.g., silicon) are identified as element 3302; the conductive material between the active electrode particles, such as carbon black, is identified as element 3303; the conventional separator is identified as element 3304; the separator of this embodiment is identified as element 3305; the inactive (deactivated) electrode material due to loss of electrical connectivity is identified as 3306; the opposing electrode is identified as element 3307; and the electrolyte is identified as 3308.

[0309] Fig.31A A schematic representation of a battery prior to use is depicted, wherein all electrode particles 3302 are electrically connected. Fig.31B A schematic representation of a battery after charging is depicted, wherein the electrode particles 3302 have a large shape change. Fig.31C A schematic representation depicting a battery with a conventional separator 3304 after some charge-discharge cycles shows electrode particles 3306 where some of the electrode particles have lost their electrical communication with the current collector and are thus inactive. Fig.31D A schematic representation depicting a battery including a conductive separator 3305 in place of a conventional separator 3304 after some charge-discharge cycles shows that some of the electrode particles have lost their conventional electrical communication with the current collector, but that the conductive separator 3305 provides new pathways for some of the electrode particles 3303. Arrows indicate the paths of electrons transferred from these particles along the conductive separator 3305 to the current collector.

[0310] The new battery described in this embodiment is not limited to conventional parallel plate batteries. An example of this battery is prepared by using the 3-d battery structure described in the inventor's US patent publication US 2012 / 0077095. 3 layers (2 cm×2 cm×0.2 cm) of the LiCoO2 cathode from MTI are placed on top of each other and perforated to make a 1 mm periodic hole. Then a ring of 0.025 mm thick PE polymer is placed between the periodic holes as an electrolyte support, and the layer is placed in a 2 cm×2 cm×1 cm aluminum tube. A copper wire with a diameter of about 0.75 mm is placed through the hole and fixed from the top and bottom by a guide. Electrolyte (a mixture of PC, EC, DMC and LiClO4 / LiPF6) is added as an electrolyte. After fixing the battery and attaching it to a galvanostat, the battery is charged at a rate as low as 10 μA starting for up to several days. Lithium metal is deposited on the copper wire forming the anode. After several charge and discharge cycles (called battery formation), the battery is ready for use for stable performance. After cycling such a conventional battery at a higher current (e.g., 1 mA), the battery will short due to the formation of lithium dendrites on the copper wires and the growth of such dendrites to the point where they contact the LiCoO2 plates. Using a shifter-layer separator design as discussed earlier prevents shorting and improves the cycle life of the battery.

[0311] The efficiency of the separator in preventing dendrite shorting was also clearly shown by fabricating a symmetric lithium coin cell and cycling it at high current. The results (experiments at room temperature, electrolyte: LP71 from Merk) showed that a 0.75 mm thick lithium foil disk could be cycled for more than 500 cycles at a flow rate of up to 10 mA and a cycle time of 5 hours without signs of shorting.

[0312] Example 7: Experimental results of an electrochemical cell having an electronically and ionically conductive layer positioned adjacent to an electrode Experiment A: An electrochemical cell was constructed from a 0.100 mm thick lithium cobalt oxide cathode and a 0.35 mm thick Li metal anode. The dielectric used for the cell was Merck LP71 (1 M LiPF6 in EC-DC-DMC 1:1:1). A 0.025 mm thick PE / PP / PE multilayer (Celgard 2325) was used as a separator. A conductive layer comprising a Ni mesh (117.6) was placed between the Li anode and the separator. The cell was 1 / 2 inch square and manufactured in a housing. The electrodes, separators, and conductive layers are cut into 1 / 2-inch diameter disc.

[0313] The battery is constructed inside the glove box. 1 / 2 inch square cells were made from Teflon. The lithium anode was made from lithium foil after rinsing with DMC and hexane. LiCoO2 foil was used as cathode. The cell was constructed with layers in the following order: wire end / stainless steel disc / Li / Ni mesh layer / Celgard separator / LiCoO2 / aluminum foil. Electrolyte was used to supersaturate the cell.

[0314] Fig.32 , 33 The cycling data, voltage versus time and current versus time, of the battery are shown in Figures 34. The battery was tested at room temperature and the voltage range was set to 3-4.2 V.

[0315] Experiment B: An electrochemical cell was constructed from a 0.100 mm thick lithium cobalt oxide cathode and a 0.35 mm thick Li metal anode. The electrolyte used for the cell was Merck LP71 (1 M LiPF6 in EC-DC-DMC 1:1:1). A 0.025 mm thick PE / PP / PE multilayer (Celgard 2325) was used as a separator. A conductive layer comprising a Cu mesh (117.6) was placed between the Li anode and the separator. The cell was 1 / 2 inch square and manufactured in a housing. The electrodes, separators, and conductive layers are cut into 1 / 2-inch diameter disc.

[0316] Fig.35 , 36 The cycling data, voltage versus time and current versus time, of the battery are shown in Figures 3 and 37. The battery was tested at room temperature and the voltage range was set to 3-4.2 V.

[0317] Experiment C: 2035 size button cells were fabricated with 0.025 mm thick PE / PP / PE multilayer separator (Celgard 2325). The electrolyte used was Merck LP50 (1 M LiPF6 in EC-EMC 1:1). LiFePO4 cathode was used and graphite anode was used. Ni mesh (117.6) was positioned between the graphite anode and separator.

[0318] Fig.38 and Fig.39 The cycling data of the battery is shown, voltage vs. time (top) and current vs. time (bottom). The battery was tested at room temperature and the voltage range was set to 2.5-4.2 V.

[0319] Experiment D: Two button cells of size 2035 were fabricated with a 0.025 mm thick PE / PP / PE multilayer separator (Celgard 2325). The electrolyte used was Merck LP50 (1 M LiPF6 in EC-EMC 1:1). A LiFePO4 cathode was used and a Li anode was used. A Ni mesh (333) was positioned between the LiFePO4 cathode and the separator.

[0320] Fig.40 and Fig.41 The cycling data, voltage vs. time and current vs. time of the battery are displayed. The battery was tested at room temperature and the voltage range was set to 2.5-4.2 V.

[0321] References U.S. Patent Nos. 8,202,649 and 8,288,034. U.S. Patent Application Publication Nos. US 2012 / 0119155, US 2012 / 0219842, and 2012 / 0183868.

[0322] Statements and Variations Regarding Incorporation by Reference All references throughout this application, such as patent documents - including issued or granted patents or equivalent documents; patent application publications and non-patent literature documents or other source materials - are hereby incorporated by reference in their entirety as if individually incorporated by reference, to the extent each reference is not at least partially inconsistent with the disclosure in this application (e.g., a partially inconsistent reference is incorporated by reference except for the partially inconsistent portion of the reference).

[0323] The terms and expressions used herein are used as terms of description rather than limitation, and there is no intention in the use of such terms and expressions to exclude any equivalent forms of the features shown and described and parts thereof, but it should be recognized that various modifications are possible within the scope of the claimed invention. Therefore, it should be understood that although the present invention is disclosed in particular by preferred embodiments, exemplary embodiments and optional features, modifications and variations of the concepts disclosed herein may be adopted by those skilled in the art, and such modifications and variations are considered to be within the scope of the invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention, and it will be obvious to those skilled in the art that the present invention can be implemented using a large number of variations of the devices, device components, and method steps set forth in this description. As is obvious to those skilled in the art, methods and devices useful for the current method may include a large number of optional composition and processing elements and steps.

[0324] All patents and publications mentioned in the specification indicate the skill level of technicians in the field to which the invention belongs. The references cited in this article are fully incorporated herein by reference to indicate the state of the art as of their filing date in some cases, and it is intended that if necessary, this information can be used in this article to exclude (e.g., deny) specific embodiments in the prior art. For example, when a compound is claimed, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (especially in the cited patent documents), are not expected to be included in the claims.

[0325] When a group of substitutes is disclosed in this article, it should be understood that all individual members and all subgroups and classes of those groups formed using substitutes are disclosed separately. When using Markush groups or other groupings in this article, all individual members and all combinations of groups and possible subcombinations of groups are expected to be included in this disclosure separately. As used in this article, "and / or" means that one, all or any combination of the items in the list separated by "and / or" is included in the list; for example, "1, 2 and / or 3" is equivalent to "1" or "2" or "3" or "1 and 2" or "1 and 3" or "2 and 3" or "1, 2 and 3".

[0326] Unless otherwise stated, each formulation or combination of the components described or illustrated can be used to practice the present invention. The specific name of the material is expected to be exemplary, and as known, those of ordinary skill in the art can name the same material differently. Those of ordinary skill in the art will understand that methods, equipment elements, starting materials and synthetic methods other than those specifically illustrated can be used in the practice of the present invention without taking excessive experiments. All functional equivalent forms known in the art of any such method, equipment element, starting material and synthetic method are expected to be included in the present invention. Whenever a range such as a temperature range, a time range or a composition range is given in the specification, all intermediate ranges and subranges and all individual values ​​included in a given range are expected to be included in the present disclosure.

[0327] It must be noted that, as used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a battery" includes a plurality of such batteries and equivalents thereof known to those skilled in the art, and so forth. The terms "a" (or "an"), "one or more," and "at least one" may also be used interchangeably herein. It should also be noted that the terms "comprising," "including," and "having" may be used interchangeably. The phrase "any of claims XX-YY" (where XX and YY refer to claim numbers) contemplates providing multiple dependent claims in optional form and is interchangeable with the phrase "as in any of claims XX-YY" in some embodiments.

[0328] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now described. Nothing herein should be construed as an admission that the present invention is not entitled to antedate such disclosure by virtue of prior invention.

[0329] Whenever a range such as an integer range, a temperature range, a time range, a composition range or a concentration range is given in the specification, all intermediate ranges and subranges and all individual values ​​included in the given range are expected to be included in the present disclosure. As used herein, ranges particularly include values ​​provided as the endpoint values ​​of the range. As used herein, ranges particularly include all integer values ​​of the range. For example, a range of 1 to 100 particularly includes the endpoint values ​​of 1 and 100. It will be understood that any subrange included in the description herein, or individual values ​​in a range or subrange may be excluded from the claims herein.

[0330] As used herein, "comprising" is synonymous with "including," "comprising," or "characterized by," and is inclusive or introductory, and does not exclude additional unrecited elements or method steps. As used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim elements. As used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. The term "comprising" in any of the descriptions herein - particularly in the description of constituent parts or in the description of elements of the device - is to be understood to include those compositions and methods consisting essentially of and consisting of the recited parts or elements. The invention illustratively described herein may suitably be practiced in the absence of any one or more elements, any one or more limitations not specifically disclosed herein.

[0331] The terms and expressions employed are used as terms of description rather than limitation, and there is no intention in the use of such terms and expressions to exclude any equivalent forms of the features shown and described or portions thereof, but it should be recognized that various modifications are possible within the scope of the claimed invention. Therefore, it should be understood that although the present invention has been particularly disclosed by preferred embodiments and optional features, those skilled in the art may adopt modifications and variations of the concepts disclosed herein, and such modifications and variations are considered to be within the scope of the invention as defined by the appended claims.

Claims

1. An electrochemical cell, comprising: a solid positive electrode, the solid positive electrode comprising a positive current collector; a solid negative electrode, the solid negative electrode comprising a negative current collector; a solid film between the negative electrode and the positive electrode; wherein the solid film comprises a solid electrolyte layer; as well as at least one electronically and ionically conductive layer between the negative electrode and the solid electrolyte layer; wherein the at least one electronically and ionically conductive layer is in direct physical contact with the solid electrolyte layer; and wherein the at least one electronically and ionically conductive layer comprises a carbon material and at least one metal or metal alloy; wherein the at least one metal or metal alloy comprises a lithium alloy; and Wherein the at least one electronically and ionically conductive layer comprises at least one coating on the solid electrolyte layer or on the negative electrode.

2. The electrochemical cell of claim 1, wherein the at least one coating is not porous.

3. The electrochemical cell of claim 1, wherein at least one coating of the electronically and ionically conductive layer is a coating of at least one metal or metal alloy on the solid electrolyte layer.

4. The electrochemical cell of claim 1, wherein at least one coating of said electronically and ionically conductive layer is a coating of said carbon material and at least one metal or metal alloy on said solid electrolyte layer.

5. The electrochemical cell of claim 1, wherein the at least one electronically and ionically conductive layer has a thickness between 10 nm and 10 μm.

6. The electrochemical cell of claim 1, wherein the at least one electronically and ionically conductive layer participates in an electrochemical reaction of the positive electrode or the negative electrode.

7. The electrochemical cell of claim 1, wherein the positive electrode comprises a lithiated active material.

8. The electrochemical cell of claim 7, wherein the positive electrode comprises a lithiated metal oxide.

9. The electrochemical cell of claim 1, wherein the negative electrode comprises a material that undergoes a shape change.

10. The electrochemical cell of claim 1, wherein the negative electrode comprises lithium metal and / or a lithium alloy.

11. The electrochemical cell of claim 1, wherein the at least one metal or metal alloy comprises silver (Ag).

12. The electrochemical cell of claim 1, comprising a lithium secondary battery, wherein the lithium secondary battery is a Li metal battery.

13. The electrochemical cell of claim 1, wherein the electrochemical cell is a rechargeable lithium battery, the rechargeable lithium battery comprises a metal coating material, and wherein the metal coating material comprises silver, aluminum, zinc, or a combination thereof.

14. The electrochemical cell of claim 1, wherein the at least one electronically and ionically conductive layer does not store and / or transport energy.

15. The electrochemical cell of claim 1, wherein the at least one electronically and ionically conductive layer is configured to reduce one of the positive electrode and the negative electrode.

16. The electrochemical cell of claim 1, wherein the at least one metal or metal alloy comprises aluminum.

17. The electrochemical cell of claim 1, wherein said at least one electronically and ionically conductive layer further comprises aluminum oxide.

18. The electrochemical cell of claim 1, wherein the at least one metal or metal alloy comprises fibers or nanofibers.

19. The electrochemical cell of claim 1, wherein said at least one electronically and ionically conductive layer comprises a coating on said negative electrode.

20. The electrochemical cell of claim 1, wherein said at least one electronically and ionically conductive layer comprises a coating on said solid electrolyte layer.

21. The electrochemical cell of claim 1, wherein at least one of the coatings is porous.

22. The electrochemical cell of claim 1, wherein the at least one electronically and ionically conductive layer is in electrical contact with an active positive electrode material or an active negative electrode material; and wherein the at least one electronically and ionically conductive layer reduces at least one of the positive electrode and the negative electrode.

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