Separator for three-dimensional battery

Abstract

To provide a device which does not require a secondary battery and other energy storage devices having greater energy density.SOLUTION: The present invention is an electrode structure for use in an energy storage device. The electrode structure comprises a group of electrodes, a group of counter-electrodes and an electrically insulating material layer separating elements of the group of electrodes from elements of the group of counter-electrodes, each element of the group of electrodes having a longitudinal axis AE that is surrounded by the electrically insulating separator layer.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates generally to structures for use in energy storage devices, energy storage devices incorporating such structures, and methods for manufacturing such structures and energy devices. [Background technology]

[0002] A rocking chair secondary battery or insertion secondary battery is a type of energy storage device in which carrier ions, such as lithium ions, sodium ions, potassium ions, calcium ions, or magnesium ions, move between a positive electrode and a negative electrode through an electrolyte. A secondary battery may comprise a single battery cell or may comprise two more battery cells electrically connected to form a battery, each battery cell comprising a positive electrode, a negative electrode, a microporous separator, and an electrolyte.

[0003] Both the positive and negative electrodes in a rocking chair battery cell comprise materials into which carrier ions can be inserted and extracted. As the cell is discharged, carrier ions are extracted from the negative electrode and inserted into the positive electrode. When the cell is charged, the reverse process occurs, and carrier ions are extracted from the positive electrode and inserted into the negative electrode.

[0004] 1 is a cross-sectional view of an electrochemical stack of an existing energy storage device, such as a non-aqueous lithium-ion battery. The electrochemical stack 1 includes a positive current collector 12, on which a positive active material layer 13 is assembled. This layer is coated with a microporous separator 14, on which an assembly of a negative current collector 15 and a negative active material layer 16 is placed. This stack may be assembled into a secondary battery by coating the negative current collector 15 with another separator layer (not shown), rolling it up, packaging it, and filling it with a non-aqueous electrolyte.

[0005] The positive and negative current collectors store the current from the respective active electrochemical electrodes and allow the current to be transferred to the environment outside the battery. A portion of the negative current collector is in physical contact with the negative active material, while a portion of the positive current collector is in physical contact with the positive active material. The current collectors do not participate in the electrochemical reaction and are therefore limited to materials that are electrochemically stable within the range of the respective electrochemical potentials of the anode and cathode.

[0006] To bring the current from the current collectors to the external battery environment, the negative and positive current collectors are typically each connected to an electrode bus, tab, tag, package feedthrough, or housing feedthrough, typically collectively referred to as a contact. One end of the contact is connected to one or more current collectors, while the other end is electrically connected through the battery packaging to the external battery environment. The negative contact is connected to the negative current collector and the positive contact is connected to the positive current collector by welding, crimping, or ultrasonic bonding, or glued in place by conductive glue.

[0007] Conventional wound batteries (see, for example, U.S. Patent Nos. 5,393,633 and 5,396,623) typically have electrode materials (active materials, binders, conductive aids) coated onto a sheet of foil and compressed prior to cell assembly. The foil on which the electrodes are coated is typically part of the current collection path. In jelly-roll type cells, such as 18650 cells or prismatic cells, the current collector foil is ultrasonically welded to an electrode bus, tab, tag, etc., which transmits current from the active material through the current collector foil and tab to the outside of the battery. Depending on the design, the tab may be present in multiple locations along a single jelly roll, or along a location at one or both ends of the current collector foil. Conventional laminated battery pouch cells have multiple plates (or foils) of active material, and the top sections of each foil are then gathered and welded together to a tab. The tab then transmits current to the outside of the battery pouch (see, for example, U.S. Patent No. 5,393,623).

[0008] 1, during the charging process, lithium exits the positive electrode cathode layer 13 and travels as lithium ions through the separator 14 to the negative electrode active material layer 16. Depending on the negative electrode active material used, the lithium ions may be intercalated (e.g., located without forming an alloy within the matrix of the negative electrode active material) or may form an alloy. During the discharging process, lithium exits the negative electrode active material layer 16 and travels through the separator 14 to the positive electrode active material layer 13. Current conductors conduct electrons from the battery contacts (not shown) to the electrodes or vice versa.

[0009] Battery separators are used to separate the anode and cathode during assembly and battery operation. Existing lithium-ion battery separators typically use thin, porous insulating materials with high ion permeability, good mechanical stability, and good chemical compatibility with the battery chemistry. Structurally, the separator should be porous enough to absorb the liquid electrolyte to achieve high ionic conductivity. It is primarily a microporous layer consisting of either a polymer membrane or a nonwoven mat.

[0010] Existing energy storage devices, such as batteries, fuel cells, and electrochemical capacitors, typically have two-dimensional layered structures (e.g., flat or spiral-wound laminates) as shown in FIG. 1, where the surface area of ​​each laminate is approximately equal to its geometric footprint (not considering porosity and surface roughness).

[0011] In the literature, three-dimensional batteries have been proposed as a way to increase battery capacity and active material utilization. It has been proposed that three-dimensional structures can be used to provide greater surface area and energy than two-dimensional layered battery structures. Producing three-dimensional energy storage devices has the advantage that greater energy can be obtained from a smaller geometric area. See, for example, Patent Document 4 and Non-Patent Document 1. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] U.S. Patent No. 6,090,505 [Patent Document 2] U.S. Patent No. 6,235,427 [Patent Document 3] US Patent Publication No. 2005 / 0008939 [Patent Document 4] International Publication No. 2008 / 089110 Brochure [Non-patent literature]

[0013] [Non-Patent Document 1] Long et al., "Three-Dimensional Battery Architectures,"Chemical Reviews,(2004),104,4463-4492 [Non-Patent Document 2] P. Arora, J. Zhang, “Battery Separators” Chemical Reviews”, 2004, 104, 4419-4462 [Non-Patent Document 3] AH Whitehead, M. Schreiber, “Current collectors for positive electrodes of lithim-based batteries” Journal of the Electrochemical Society,” 152(11)A2105-A2113(2005) Summary of the Invention [Problem to be solved by the invention]

[0014] Despite the advances made to date, there remains a need for secondary batteries and other energy storage devices with greater energy densities. [Means for solving the problem]

[0015] Various aspects of the invention include providing three-dimensional structures for use in energy storage devices such as batteries, fuel cells and electrochemical capacitors. Advantageously, and according to one aspect of the invention, the ratio of electrode active materials to other components of the energy storage device, i.e., to the non-active material components of the energy storage device, may be increased. As a result, energy storage devices comprising three-dimensional structures according to the invention may have a greater energy density. Such energy storage devices may also provide higher energy recovery rates for a particular amount of energy stored than two-dimensional energy storage devices, such as by minimizing or reducing the transport distance of electrons or ion transfer between the positive and negative electrodes. These devices may be more suitable for miniaturization and for applications where the geometric area available for a device is limited and / or the energy density requirements are higher than can be achieved with layered devices.

[0016] Briefly, therefore, one aspect of the invention is an electrode structure for use in an energy storage device. The electrode structure comprises a population of electrodes having an electrode active material layer and a population of counter electrodes having a counter electrode active material layer. The population of electrodes is arranged in a first direction, alternating with a population of counter electrodes. Each element of the population of electrodes has a bottom, a top, and a length L. E and width W E and height H E and a longitudinal axis A extending from the bottom to the top of the element in a direction intersecting the first direction. E and each element of the electrode group has a length L E is its longitudinal axis A E The width W of each element of the electrode group is measured in the direction E is measured in the first direction and is the height H of each element of the electrode group E is the longitudinal axis A of the element E and the L of each element of the electrode group is measured in a direction perpendicular to the first direction. E and W E and H E and H of each element of the electrode group are at least 5:1. E and WE The ratio of the longitudinal axis A of each element of the electrode group is between 0.4:1 and 1000:1. E is surrounded by an electrically insulating separator layer, which comprises a microporous separator material layer comprising a particulate material and a binder between the elements of the electrode group and the elements of the counter-electrode group, the microporous separator material layer having a void fraction of at least 20% by volume.

[0017] A further aspect of the invention is an electrode structure for use in an energy storage device, comprising an electrode population having an electrode active material layer and a counter electrode population having a counter electrode active material layer. The electrode population is arranged in alternating fashion with a counter electrode population along a first direction. Each element of the electrode population has a bottom, a top, and a length L. E and width W E and height H E and a longitudinal axis A extending from the bottom to the top of the element in a direction intersecting the first direction. E and each element of the electrode group has a length L E is its longitudinal axis A E The width W of each element of the electrode group is measured in the direction E is measured in the first direction and is the height H of each element of the electrode group E is the longitudinal axis A of the element E and the L of each element of the electrode group is measured in a direction perpendicular to the first direction. E and W E and H E and H of each element of the electrode group are at least 5:1. E and W E The ratio of the longitudinal axis A of each element of the electrode group is between 0.4:1 and 1000:1. E is surrounded by an electrically insulating separator layer, which comprises a microporous separator material layer comprising a particulate material and a binder between the elements of the electrode group and the elements of the counter-electrode group, the microporous separator material layer having a void fraction of at least 20% by volume.

[0018] Another aspect of the present invention is an electrode stack comprising at least two electrode structures, each of which comprises an electrode group having an electrode active material layer and a counter electrode group having a counter electrode active material layer. The electrode groups are arranged alternately with the counter electrode groups along a first direction. Each element of the electrode group has a bottom, a top, and a length L. E and width W E and height H E and a longitudinal axis A extending from the bottom to the top of the element in a direction intersecting the first direction. E and each element of the electrode group has a length L E is its longitudinal axis A E The width W of each element of the electrode group is measured in the direction E is measured in the first direction and is the height H of each element of the electrode group E is the longitudinal axis A of the element E and the L of each element of the electrode group is measured in a direction perpendicular to the first direction. E and W E and H E and H of each element of the electrode group are at least 5:1. E and W E The ratio of the longitudinal axis A of each element of the electrode group is between 0.4:1 and 1000:1. E is surrounded by an electrically insulating separator layer, which comprises a microporous separator material layer comprising a particulate material and a binder between the elements of the electrode group and the elements of the counter-electrode group, the microporous separator material layer having a void fraction of at least 20% by volume.

[0019] Another aspect of the present invention is a secondary battery comprising a battery case, a non-aqueous electrolyte, and an electrode structure. The electrode structure comprises an electrode group having an electrode active material layer, and a counter electrode group having a counter electrode active material layer. The electrode group and the counter electrode group are arranged alternately along a first direction. Each element constituting the electrode group has a bottom, a top, and a length L E and width W E and height H E and a longitudinal axis A extending from the bottom to the top of the element in a direction intersecting the first direction. E and each element of the electrode group has a length LE is its longitudinal axis A E The width W of each element of the electrode group is measured in the direction E is measured in the first direction and is the height H of each element of the electrode group E is the longitudinal axis A of the element E and the L of each element of the electrode group is measured in a direction perpendicular to the first direction. E and W E and H E and H of each element of the electrode group are at least 5:1. E and W E The ratio of the longitudinal axis A of each element of the electrode group is between 0.4:1 and 1000:1. E is surrounded by an electrically insulating separator layer, which comprises a microporous separator material layer comprising a particulate material and a binder between the elements of the electrode group and the elements of the counter-electrode group, the microporous separator material layer having a void fraction of at least 20% by volume.

[0020] Other objects and features will be in part apparent and in part pointed out hereinafter. [Brief description of the drawings]

[0021] [Figure 1] FIG. 1 is a cross-sectional view of a cell of an electrochemical stack of a typical prior art two-dimensional energy storage device such as a lithium ion battery. [Diagram 2] FIG. 1 is a perspective view of one embodiment of an electrode structure of the present invention, with a portion cut away to show the internal structure. [Diagram 3] 3 is a partial cross-sectional view of the electrode structure taken along a plane including line 3-3 in FIG. 2. [Figure 4] FIG. 3 is a partial perspective view showing a subassembly of the electrode structure of FIG. 2. [Diagram 5] FIG. 5 is a plan view of a subassembly of the electrode structure taken along line 5 in FIG. 4. [Figure 6] FIG. 5 is a plan view of a subassembly of the electrode structure taken along line 6 in FIG. 4. [Figure 7]7 is a cross-sectional view showing a subassembly of the electrode structure taken along a plane including line 7-7 in FIG. 5. [Figure 8] 8 is a cross-sectional view showing a subassembly of the electrode structure taken along a plane including line 8-8 in FIG. 6. [Figure 9] 3 is a partial perspective view of a subassembly of the electrode structure of FIG. 2, with a portion cut away to show the internal structure. FIG. [Figure 10] FIG. 2 is an exploded view of a three-dimensional secondary battery of the present invention. [Figure 11] FIG. 11 is a partial perspective view showing the assembled three-dimensional secondary battery of FIG. 10. [Figure 12] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 13] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 14] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 15] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 16] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 17] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 18] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 19] 3 is a partial perspective view of an alternative embodiment of a subassembly of the electrode structure of FIG. 2, with a portion cut away to reveal the internal structure. FIG. [Figure 20] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 21] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Figure 22] 3 is a cross-sectional view of an alternative embodiment of an electrode structure taken along a plane including line 3-3 of FIG. 2. [Diagram 23] 5 is a partial perspective view of a subassembly of an alternative embodiment of the electrode structure taken along line 5 of FIG. 4, with a portion cut away to show the internal structure. [Figure 24] 6 is a partial perspective view of a subassembly of an alternative embodiment of the electrode structure taken along line 6 of FIG. 4, with a portion cut away to show the internal structure. [Figure 25A] FIG. 2 is a cross-sectional view of an alternative embodiment of an electrode (positive or negative) of the present invention. [Figure 25B] FIG. 2 is a cross-sectional view of an alternative embodiment of an electrode (positive or negative) of the present invention. [Figure 25C] FIG. 2 is a cross-sectional view of an alternative embodiment of an electrode (positive or negative) of the present invention. [Figure 25D] FIG. 2 is a cross-sectional view of an alternative embodiment of an electrode (positive or negative) of the present invention. [Figure 25E] FIG. 2 is a cross-sectional view of an alternative embodiment of an electrode (positive or negative) of the present invention. [Figure 26] FIG. 2 is a cross-sectional view of an alternative embodiment of an electrode stack of the present invention. [Figure 27] FIG. 2 is a cross-sectional view of an alternative embodiment of an electrode stack of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Corresponding reference characters indicate corresponding parts or components throughout the drawings.

[0023] Among the various aspects of the present invention, noteworthy are three-dimensional structures that offer particular advantages when incorporated into energy storage devices such as batteries, capacitors, and fuel cells. For example, such structures may be incorporated into secondary batteries in which the positive electrode, negative electrode, and / or separator are essentially non-layered. In a preferred embodiment, such structures are incorporated into secondary batteries in which carrier ions (e.g., selected from lithium ions, sodium ions, potassium ions, calcium ions, and magnesium ions) migrate between the positive and negative electrodes.

[0024] In general, the three-dimensional structure comprises a group of electrodes, a group of counter electrodes, and a separator material for electrically insulating elements of the group of electrodes from elements of the group of counter electrodes. The group of electrodes and the group of counter electrodes are arranged in an alternating manner, with each element of the group of electrodes being substantially between two elements of the group of counter electrodes, and each element of the group of counter electrodes being substantially between two elements of the group of electrodes. For example, with the exception of the first and last electrodes or counter electrodes in the alternating series of electrodes, in one embodiment, each electrode is between two counter electrodes, and each counter electrode is between two electrodes in the alternating series of electrodes.

[0025] In some embodiments, the members of the electrode population include an electrode active material layer, an electrode current collector, and an electrode backbone supporting the electrode active material layer and the electrode current collector. Similarly, in some embodiments, the members of the counter electrode population include a counter electrode active material layer, a counter electrode current collector, and a counter electrode backbone supporting the counter electrode active material layer and the counter electrode current collector.

[0026] Each element of the electrode group has a bottom, a top, and a longitudinal axis (A ) that extends generally perpendicular to the direction in which the alternating sequence of electrodes and counterelectrodes proceeds from bottom to top of each element. E ) and each element of the electrode group has a longitudinal axis (A E ) along the length (L E ) and the width (W E ) and length (L E ) and width (W E ) is measured perpendicular to the direction of each measurement (H E Each element of the electrode group has a circumference (P E ) is also available.

[0027] The length of the electrode group element (L E ) will vary depending on the energy storage device and its intended use. In general, however, the elements of the electrode group typically have a length (L EFor example, in one such embodiment, the elements of the electrode group have a length (L E By way of further example, the elements of the electrode population in one such embodiment have a length (L E ).

[0028] In addition, the width of the electrode group elements (W E The width (W) of each electrode element will also vary depending on the energy storage device and its intended use. In general, however, each element of the electrode group will typically have a width (W) within the range of about 0.01 mm to 2.5 mm. E For example, in one embodiment, each element of the electrode group has a width (W E ) may range from about 0.025 mm to about 2 mm. By way of further example, the width (W E ) will be in the range of about 0.05 mm to about 1 mm.

[0029] In addition, the height of the electrode group elements (H E The height (H) also varies depending on the energy storage device and its intended use. In general, however, the elements of the electrode group typically have a height (H) within the range of about 0.05 mm to about 10 mm. E For example, in one embodiment, each element of the electrode group has a height (H E ) may range from about 0.05 mm to about 5 mm. By way of further example, the height (H E ) will be in the range of about 0.1 mm to about 1 mm.

[0030] Similarly, the perimeter of the electrode group elements (P E ) will also vary depending on the energy storage device and its intended use. In general, however, the elements of the electrode group typically have a circumference (P E For example, in one embodiment, the perimeter (P E) may range from about 0.1 mm to about 15 mm. By way of further example, the circumference (P E ) will be in the range of about 0.5 mm to about 10 mm.

[0031] In general, the elements of the electrode group are E ) and its height (H E ) E For example, in one embodiment, in each element of the electrode group, L E and W E and H E and each of the L E and W E and L are at least 5:1, respectively. E and H E and the ratio of L to L is at least 5:1, respectively. E and W E and H E and each of the L is at least 10:1. E and W E and H E is at least 15:1. By way of further example, in one embodiment, in each element of the electrode population, E and W E and H E Each of the ratios is at least 20:1.

[0032] Furthermore, in general, the elements of the electrode group are arranged such that their perimeter (P E ) E For example, in one embodiment, each element of the electrode group preferably has L E and P E and L are each at least 1.25:1. E and P E and L are each at least 2.5:1.E and P E and the ratio of each is at least 3.75:1.

[0033] In one embodiment, the height (H E ) and width (W E ) is at least 0.4:1, respectively. For example, in one embodiment, in each element of the electrode group, E and W E and H in an embodiment have a ratio of at least 2:1. E and W E and H in an embodiment have a ratio of at least 10:1. E and W E The ratio of H to H is at least 20:1. E and W E The ratio of H to H is generally less than 1,000:1. E and W E and H in one embodiment are each less than 500:1. E and W E and H in one embodiment are each less than 100:1. E and W E and H E and W E and the ratio of is within the range of about 2:1 to about 100:1, respectively.

[0034] Each element of the counterelectrode group has a bottom, a top, and a longitudinal axis (A ) that extends from the bottom to the top of each element generally perpendicular to the direction in which the alternating sequence of electrodes and counterelectrodes proceeds. CE ). Furthermore, each element of the counter electrode group has a longitudinal axis (A CE ) along the length (L CE ) and the width (W CE ) and length (L CE ) and width (WCE ) is measured perpendicular to the direction of each measurement (H CE Each element of the counter electrode group has a circumference (P CE ) is also available.

[0035] The length of the counter electrode group element (L CE ) will vary depending on the energy storage device and its intended use. In general, however, each element of the counter electrode population typically has a length (L CE For example, in one such embodiment, each member of the counter electrode population has a length (L CE By way of further example, each member of the counter electrode population in one such embodiment has a length (L CE ).

[0036] Also, the width of the counter electrode group element (W CE The width (W) of the counter electrode assembly also varies depending on the energy storage device and its intended use. In general, however, the elements of the counter electrode assembly typically have a width (W) within the range of about 0.01 mm to 2.5 mm. CE For example, in one embodiment, each element of the counter electrodes has a width (W CE ) may range from about 0.025 mm to about 2 mm. By way of further example, the width (W CE ) will be in the range of about 0.05 mm to about 1 mm.

[0037] In addition, the height of the counter electrode group elements (H CE The height (H ) also varies depending on the energy storage device and its intended use. In general, however, the elements of the counter electrode population typically have a height (H ) within the range of about 0.05 mm to about 10 mm. CE For example, in one embodiment, each element of the counter electrode group has a height (H CE) may range from about 0.05 mm to about 5 mm. By way of further example, the height (H CE ) will be in the range of about 0.1 mm to about 1 mm.

[0038] In addition, the outer circumference of the counter electrode group element (P CE ) will also vary depending on the energy storage device and its intended use. In general, however, the elements of the counter electrode population typically have a circumference (P CE For example, in one embodiment, the perimeter (P CE ) may range from about 0.1 mm to about 15 mm. By way of further example, the circumference (P CE ) will be in the range of about 0.5 mm to about 10 mm.

[0039] In general, each element of the counter electrode group has a width (W CE ) and its height (H CE ) CE For example, in one embodiment, in each member of the counter electrode population, L CE and W CE and H CE and each of the L CE and W CE The ratio of L to L is at least 5:1, CE and H CE (The ratio of L to L is at least 5:1.) By way of further example, in one embodiment, in each member of the counter electrode population, CE and W CE and H CE is at least 10:1. By way of further example, in one embodiment, in each member of the counter electrode population, CE and W CE and H CE is at least 15:1. By way of further example, in one embodiment, in each member of the counter electrode population, CE and W CEand H CE Each of the ratios is at least 20:1.

[0040] Furthermore, in general, the elements of the counter electrode group are CE ) CE ) and, for example, in one embodiment, in each member of the counter electrode population, L CE and P CE and L are each at least 1.25:1. CE and P CE By way of further example, in one embodiment, the ratio of L to L in each member of the counter electrode population is at least 2.5:1. CE and P CE and the ratio of each is at least 3.75:1.

[0041] In one embodiment, the height (H CE ) and width (W CE ) is at least 0.4:1, respectively. For example, in one embodiment, in each member of the counter electrode population, CE and W CE By way of further example, in one embodiment, the ratio of H CE and W CE By way of further example, in one embodiment, the ratio of H CE and W CE The ratio of H to H is at least 20:1 for each member of the counter electrode population. CE and W CE For example, in one embodiment, the ratio of H CE and W CE and H in one embodiment are each less than 500:1. CE and W CE and H in one embodiment are each less than 100:1.CE and W CE By way of further example, in one embodiment, the ratio of H CE and W CE and the ratio ranges from about 2:1 to about 100:1, respectively.

[0042] To electrically insulate the electrode group elements from the counter-electrode group, (i) the electrode group elements are aligned along their longitudinal axis (A E ) with a layer of electrically insulating separator material, and (ii) the elements of the counter electrode group are CE ) with a layer of electrically insulating separator material, or (iii) the elements of the electrode group and the elements of the counter-electrode group are surrounded by a layer of electrically insulating material along their respective longitudinal axes. For example, in one embodiment, the longitudinal axis (A E ) is surrounded by a layer of electrically insulating material. By way of further example, in some embodiments, the longitudinal axis (A CE ) is surrounded by a layer of electrically insulating material. By way of further example, in some embodiments, the longitudinal axis (A CE ) and the longitudinal axis (A CE ) is surrounded by a layer of electrically insulating material.

[0043] In certain embodiments, the electrically insulating material layer has a thickness of at least about 5 micrometers. Generally, however, the electrically insulating material layer has a thickness (at least in the area that separates the element of the electrode group from the nearest element of the counter electrode group) that does not exceed about 100 micrometers. For example, in certain embodiments, the electrically insulating material layer has a thickness (at least in the area that separates the element of the electrode group from the nearest element of the counter electrode group) in the range of about 5 micrometers to about 50 micrometers. By way of further example, the electrically insulating material layer in certain embodiments has a thickness (at least in the area that separates the element of the electrode group from the nearest element of the counter electrode group) in the range of about 10 micrometers to about 35 micrometers. By way of further example, the electrically insulating material layer in certain embodiments has a thickness (at least in the area that separates the element of the electrode group from the nearest element of the counter electrode group) in the range of about 15 micrometers to about 30 micrometers.

[0044] The electrically insulating material layer separating the electrode active material layer of the electrode group element and the counter-electrode active material layer of the counter-electrode group element during charging or discharging operation comprises a microporous separator material. For example, in one embodiment, the microporous separator material constitutes at least 70% by volume of the electrically insulating separator material layer between the electrode group element and the counter-electrode group element, without taking into account the porosity of the microporous separator material. As a further example, in one embodiment, the microporous separator material constitutes at least 75% by volume of the electrically insulating separator material layer between the electrode group element and the counter-electrode group element, without taking into account the porosity of the microporous separator material. As a further example, in one embodiment, the microporous separator material constitutes at least 80% by volume of the electrically insulating separator material layer between the electrode group element and the counter-electrode group element, without taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, the microporous separator material constitutes at least 85% by volume of the electrically insulating separator material layer between the element of the electrode group and the element of the counter-electrode group, without taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, the microporous separator material constitutes at least 90% by volume of the electrically insulating separator material layer between the element of the electrode group and the element of the counter-electrode group, without taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, the microporous separator material constitutes at least 95% by volume of the electrically insulating separator material layer between the element of the electrode group and the element of the counter-electrode group, without taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, the microporous separator material constitutes at least 99% by volume of the electrically insulating separator material layer between the element of the electrode group and the element of the counter-electrode group, without taking into account the porosity of the microporous separator material.

[0045] In some embodiments, the microporous separator material includes a particulate material and a binder, and has a porosity (void fraction) of at least about 20% by volume. The pores of the microporous separator material have a diameter of at least 50 Å, and typically fall within the range of about 250 Å to 2,500 Å. The microporous separator material typically has a porosity of less than about 75%. In some embodiments, the microporous separator material has a porosity (void fraction) of at least about 25% by volume. In some embodiments, the microporous separator material has a porosity of about 35-55%.

[0046] The binder of the microporous separator material may be selected from a wide range of inorganic or polymeric materials. For example, in some embodiments, the binder is an organic material selected from the group consisting of silicates, phosphates, aluminates, aluminosilicates, and hydroxides such as magnesium hydroxide, calcium hydroxide, and others. For example, in some embodiments, the binder is a fluoropolymer derived from monomers containing vinylidene fluoride, hexafluoropropylene, tetrafluoropropene, and the like. In another embodiment, the binder is a polyolefin such as polyethylene, polypropylene, or polybutene, with any range of variable molecular weights and molecular densities. In another embodiment, the binder is selected from the group consisting of ethylene-diene-propene terpolymers, polystyrene, polymethylmethacrylate, polyethylene glycol, polyvinyl acetate, polyvinyl butyral, polyacetal, and polyethylene glycol diacrylate. In another embodiment, the binder is selected from the group consisting of methyl cellulose, carboxymethyl cellulose, styrene rubber, butadiene rubber, styrene-butadiene rubber, isoprene rubber, polyacrylamide, polyvinyl ether, polyacrylic acid, polymethacrylic acid, and polyethylene oxide. In another embodiment, the binder is selected from the group consisting of acrylates, styrenes, epoxies, and silicones. In another embodiment, the binder is a copolymer or blend of two or more of the above polymers.

[0047] Additionally, the particulate material comprising the microporous separator material may be selected from a wide variety of materials. Generally, such materials have relatively low electronic and ionic conductivity at operating temperatures and do not corrode under the operating voltages of the battery electrodes or current collectors that contact the microporous separator material. For example, in one embodiment, the particulate material is in the range of 1×10 -4 By way of further example, in certain embodiments, the particulate material has a carrier ion (e.g., lithium) conductivity of less than 1×10 -5 By way of further example, in certain embodiments, the particulate material has a carrier ion conductivity of less than 1×10 -6 Examples of particulate materials are particulate polyethylene, polypropylene, TiO 2 -polymer composites, silica aerogels, fumed silica, silica gels, silica hydrogels, silica xerogels, silica sols, colloidal silica, alumina, titania, magnesia, kaolin, talc, diatomaceous earth, calcium silicate, aluminum silicate, calcium carbonate, magnesium carbonate, or combinations thereof. For example, in certain embodiments, the particulate material may be TiO 2 , SiO 2 , Al 2 O 3 , GeO 2 , B 2 O 3 , Bi 2 O 3 , BaO, ZnO, ZrO 2 , BN, Si 3 N 4 , Ge 3 N 4 For example, see Non-Patent Document 2. In some embodiments, the particulate material has an average particle size of about 20 nm to 2 micrometers, more typically 200 nm to 1.5 micrometers. In some embodiments, the particulate material has an average particle size of about 500 nm to 1 micrometer.

[0048] In an alternative embodiment, the particulate material comprised of the microporous separator material may be bound by techniques such as sintering, bonding, curing, etc., while maintaining a desired void fraction for electrolyte infiltration to provide ionic conductivity for the battery to function.

[0049] The microporous separator material may be deposited by, for example, electrophoretic deposition of a particulate separator material, where the particles are coalesced by surface energies such as electrostatic attraction or van der Waals forces, slurry deposition of the particulate separator material (including spin coating or spray coating), screen printing, dip coating, and electrostatic spray deposition. A binder may be included in the deposition process, for example, the particulate material may be slurry deposited with a dissolved binder that precipitates upon solvent evaporation, electrophoretically deposited in the presence of a dissolved binder material, co-electrophoretically deposited with a binder and insulating particles, etc. Alternatively, or additionally, the binder may be added after the particles are deposited in or on the electrode structure, for example, the particulate material may be dispersed in an organic binder solution and dip coated or spray coated, followed by drying, melting, or crosslinking the binder material to provide adhesive strength.

[0050] In the assembled energy storage device, the microporous separator material is infiltrated with a non-aqueous electrolyte suitable for use as a secondary battery electrolyte. Typically, the non-aqueous electrolyte comprises a lithium salt dissolved in an organic solvent. An example of a lithium salt is LiClO 4 , LiBF 4 , LiPF 6 , LiAsF 6 , inorganic lithium salts such as LiCl and LiBr, and LiB(C 6 H 5 ) 4 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 CF 3 ) 3 , LiNSO 2 CF 3 , LiNSO2 CF 5 , LiNSO 2 C 4 F 9 , LiNSO 2 C 5 F 11 , LiNSO 2 C 6 F 13 and LiNSO 2 C 7 F 15 Examples of organic lithium salts include organic lithium salts such as cyclic esters, chain esters, cyclic ethers, and chain ethers. Specific examples of cyclic esters include propylene carbonate, butylene carbonate, γ-butyrolactone, vinylene carbonate, 2-methyl-γ-butyrolactone, acetyl-γ-butyrolactone, and γ-valerolactone. Specific examples of chain esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl butyl carbonate, methyl propyl carbonate, ethyl butyl carbonate, ethyl propyl carbonate, butyl propyl carbonate, alkyl propionate, dialkyl malonate, and alkyl acetate. Specific examples of cyclic ethers include tetrahydrofuran, alkyl tetrahydrofuran, dialkyl tetrahydrofuran, alkoxy tetrahydrofuran, dialkoxy tetrahydrofuran, 1,3-dioxolane, alkyl-1,3-dioxolane, and 1,4-dioxolane. Specific examples of chain ethers include 1,2-dimethoxyethane, 1,2-diethoxyethane, diethyl ether, ethylene glycol dialkyl ether, diethylene glycol dialkyl ether, triethylene glycol dialkyl ether and tetraethylene glycol dialkyl ether.

[0051] In one embodiment, the electrode population is a group of negative electrodes and the counterelectrode population is a group of positive electrodes. In this embodiment, the longitudinal axis A of the elements of the electrode population E , length L E , width W E , height H E and outer perimeter P E are the longitudinal axes A of the negative electrode group elements, respectively. NE , length L NE , width W NE, height H NE and outer perimeter P NE and the longitudinal axis A of the element of the counter electrode group CE , length L CE , width W CE , height H CE and outer perimeter P CE are the longitudinal axes A of the positive pole group elements, respectively. PE , length L PE , width W PE , height H PE and outer perimeter P PE Corresponds to.

[0052] In an alternative embodiment, the electrode population is a group of positive electrodes and the counterelectrode population is a group of negative electrodes. Thus, in this embodiment, the longitudinal axis A of the elements of the electrode population E , length L E , width W E , height H E and outer perimeter P E are the longitudinal axes A of the positive pole group elements, respectively. PE , length L PE , width W PE , height H PE and outer perimeter P PE and the longitudinal axis A of the element of the counter electrode group CE , length L CE , width W CE , height H CE and outer perimeter P CE are the longitudinal axes A of the negative electrode group elements, respectively. NE , length L NE , width W NE , height H NE and outer perimeter P NE Corresponds to.

[0053] Referring now to FIG. 2, in one embodiment of the present invention, the electrode structure 20 comprises a group of negative electrodes 21 and a group of positive electrodes 22. For ease of explanation, in FIG. 2, the negative electrode group includes four elements 21 and the positive electrode group includes four elements 22, but in practice, the negative electrode group and the positive electrode group may each include a greater or lesser number of elements. For example, in one embodiment, the negative electrode group and the positive electrode group included in the electrode structure of the present invention may each include at least five elements. As a further example, in one embodiment, the negative electrode group and the positive electrode group each include at least 10 elements. As a further example, in one embodiment, the negative electrode group and the positive electrode group each include at least 50 elements. As a further example, in one embodiment, the negative electrode group and the positive electrode group each include at least 100 elements.

[0054] Regardless of the number of elements, the elements 21 of the negative electrode group and the elements 22 of the positive electrode group are interdigitated and arranged in an alternating sequence in the direction D. As shown in FIG. 2, each element 21 of the negative electrode group is between two elements 22 of the positive electrode group, with one exception, and each element 22 of the positive electrode group is between two elements 21 of the negative electrode group, with one exception. More generally, in some embodiments, the positive electrode group and the negative electrode group each have N elements, N-1 positive electrode group elements each are between two negative electrodes, N-1 negative electrode group elements each are between two positive electrodes, and N is at least 2. For example, in some embodiments, N is at least 4 (as shown in FIG. 2), at least 5, at least 10, at least 25, at least 50, or even at least 100.

[0055] In an alternative embodiment, with the series of interdigitated electrodes progressing in direction D, each element 21 of the negative electrode population is between two elements 22 of the positive electrode population such that the series of interdigitated electrodes begins and ends with a positive electrode 22, with each negative electrode 21 being between two positive electrodes 22 (e.g., the series of electrodes has a repeating sequence as follows: positive electrode, negative electrode, positive electrode, negative electrode, positive electrode, ...). For example, in one such embodiment, the negative electrode population has N elements and the positive electrode population has N+1 elements, each negative electrode is between two positive electrodes, and N is at least 5, at least 10, at least 25, at least 50, or even at least 100.

[0056] In another alternative embodiment, each element 22 of the positive electrode population is between two elements 21 of the negative electrode population, such that, for example, the series of interdigitated electrodes proceeds in direction D, beginning and ending with a negative electrode 21, with each positive electrode 22 being between two negative electrodes 21 (e.g., the series of electrodes has a repeating sequence as follows: negative electrode, positive electrode, negative electrode, positive electrode, negative electrode, ...). In one such embodiment, the positive electrode population has N elements, the negative electrode population has N+1 elements, each positive electrode is between two negative electrodes, and N is at least 5, at least 10, at least 25, at least 50, or even at least 100.

[0057] 2, each element 21 of the negative electrode group is directly connected to and extends from a negative electrode bus 23 that collects current from each element 21 of the negative electrode group. The negative electrode bus 23 may then be used to electrically connect each element 21 of the negative electrode group to a negative terminal of an energy storage device (not shown), or to an external energy supply (not shown), or to an external energy consumer (not shown).

[0058] Each element 22 of the positive electrodes is connected to and extends from a positive electrode bus 24 that sinks current from each element 22 of the positive electrodes and may be used to electrically connect each element 22 of the positive electrodes to a positive terminal of an energy storage device (not shown), or to an external energy supply (not shown), or to an external energy consumer (not shown).

[0059] The negative and positive buses 23, 24 may comprise any of a wide variety of conductive materials. For example, the negative and positive buses 23, 24 may independently comprise conductive ceramics, glasses, polymers, semiconductors, or metals to electrically connect the negative and positive electrode populations of elements to the negative and positive conductive paths 25, 26, respectively. As a further example, the negative and positive buses 23, 24 in some embodiments each independently comprise a conductive material such as silicon, carbon, carbon composites, metal silicides, and the like. Examples of materials for the positive buses include aluminum, carbon, chromium, gold, nickel, NiP, palladium, platinum, rhodium, ruthenium, silicon-nickel alloys, titanium, alloys of one or more of these, and combinations thereof. Examples of materials for the negative buses include copper, nickel, chromium, titanium, tungsten, cobalt, carbon, alloys of one or more of these, and combinations thereof. Materials for the positive and negative buses may be deposited by any of a wide variety of well-known metal deposition processes, such as evaporation, sputtering, electroless plating, immersion plating, electroplating, and the like. In certain embodiments, the conductive portions of the positive and negative buses may comprise the same material. In other embodiments, the conductive portions of the positive and negative buses may comprise materials that differ in composition. In certain embodiments, the positive and / or negative buses comprise a non-conductive core that is partially or completely covered by a shell of conductive material, and further, in such embodiments where the positive and negative buses comprise a non-conductive core that is partially or completely covered by a shell of conductive material, the non-conductive cores of the positive and negative buses may have the same composition even if the compositions of the conductive shells are different.

[0060] An electrically insulating separator layer 43 surrounds and electrically insulates each element 21 of the negative electrode population from each element 22 of the positive electrode population, and electrically insulates the negative electrode bus 23 from the positive electrode bus 24. Between adjacent negative electrode / positive electrode pairs (i.e., the negative electrode / positive electrode pairs that provide the shortest distance for carrier ions to travel from a given element of the negative electrode population to an element of the positive electrode population, or vice versa, during charging or discharging operations), the electrically insulating separator layer 43 comprises a microporous separator material capable of being infiltrated with a non-aqueous electrolyte as described above; for example, as detailed above, in certain embodiments, the microporous separator material comprises pores having a diameter of at least 50 Å, more typically within the range of about 2,500 Å, and a porosity within the range of about 25% to about 75%, more typically within the range of about 35-55%.

[0061] For example, in one embodiment, at least 70% by volume of the electrically insulating separator material layer 43 between the element 21 of the negative electrode population and the element 22 of the positive electrode population (i.e., the "adjacent pair") for ion exchange during a charge or discharge cycle is microporous separator material, without taking into account the porosity of the microporous separator material; in other words, the microporous separator material constitutes at least 70% by volume of the electrically insulating material between the element 21 of the negative electrode population and the element 22 of the positive electrode population. By way of further example, in one embodiment, at least 75% by volume of the electrically insulating separator material layer between the adjacent pair of the element 21 of the negative electrode population and the element 22 of the positive electrode population, without taking into account the porosity of the microporous separator material. By way of further example, in one embodiment, at least 80% by volume of the electrically insulating separator material layer between the adjacent pair of the element 21 of the negative electrode population and the element 22 of the positive electrode population, without taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, without taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 85% by volume of the electrically insulating separator material layer between adjacent pairs of elements 21 of the negative electrode population and elements 22 of the positive electrode population. By way of further example, in some embodiments, without taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 90% by volume of the electrically insulating separator material layer between adjacent pairs of elements 21 of the negative electrode population and elements 22 of the positive electrode population. By way of further example, in some embodiments, without taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 95% by volume of the electrically insulating separator material layer between adjacent pairs of elements 21 of the negative electrode population and elements 22 of the positive electrode population. As a further example, in one embodiment, not taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 99% by volume of the electrically insulating separator material layer between adjacent pairs of elements 21 of the negative electrode group and elements 22 of the positive electrode group.

[0062] 3, in one embodiment, each element 21 of the negative electrode group comprises a negative electrode backbone 51, a negative electrode current collector layer 47, and a negative electrode active material layer 49. The negative electrode active material layer 49 is bounded by outer sides 61, 63, a front surface 65, and a back surface 67. Similarly, each element 22 of the positive electrode group comprises a positive electrode backbone 52, a positive electrode current collector layer 48, and a positive electrode active material layer 50. The positive electrode active material layer 50 is bounded by outer sides 61, 63, a front surface 65, and a back surface 67. Each element 21 of the negative electrode group is separated from each element 22 of the positive electrode group by a longitudinal axis A of each element 21 of the negative electrode group. NE and the longitudinal axis A of each element 22 of the positive electrode group PE are separated by an electrically insulating separator layer 43 that surrounds them along at least a portion of their respective lengths.

[0063] Between the opposing outer surfaces 61, 62 and 63, 64 of elements 21, 22, respectively, the electrically insulating material layer 43 comprises a microporous separator material (as described above). For example, in one embodiment, at least 70% by volume of the electrically insulating separator material layer 43 between the opposing outer surfaces 61, 62 and 63, 64 of each of elements 21, 22 comprises a microporous separator material (as described above), not taking into account the porosity of the microporous separator material. By way of further example, in one embodiment, at least 75% by volume of the electrically insulating separator material layer 43 between the opposing outer surfaces 61, 62 and 63, 64 of elements 21, 22, respectively, comprises a microporous separator material (as described above), not taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, the microporous separator material constitutes at least 80% by volume of the electrically insulating separator material layer between opposing outer surfaces 61, 62 and 63, 64 of elements 21, 22, respectively, and comprises microporous separator material (as described above), without taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, the microporous separator material constitutes at least 85% by volume of the electrically insulating separator material layer between opposing outer surfaces 61, 62 and 63, 64 of elements 21, 22, respectively, and comprises microporous separator material (as described above), without taking into account the porosity of the microporous separator material. As a further example, in one embodiment, not taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 90 volume % of the electrically insulating separator material layer between the opposing outer surfaces 61, 62 and between the opposing outer surfaces 63, 64 of elements 21, 22, respectively, and includes microporous separator material (as described above).By way of further example, in some embodiments, the microporous separator material constitutes at least 95% by volume of the electrically insulating separator material layer between opposing outer surfaces 61, 62 and 63, 64 of elements 21, 22, respectively, and comprises microporous separator material (as described above), without taking into account the porosity of the microporous separator material. By way of further example, in some embodiments, the microporous separator material constitutes at least 99% by volume of the electrically insulating separator material layer between opposing outer surfaces 61, 62 and 63, 64 of elements 21, 22, respectively, and comprises microporous separator material (as described above), without taking into account the porosity of the microporous separator material.

[0064] During a discharging process, lithium ions (or other carrier ions such as sodium, potassium, calcium or magnesium ions) leave the negative electrode active material layer 49 at the outer surfaces 61, 63, travel through the microporous separator material comprised of the electrically insulating separator layer 43, and enter the positive electrode active material layer 50 at the outer surfaces 62, 64. During a charging process, lithium ions (or other carrier ions) leave the positive electrode active material layer 50 at the outer surfaces 62, 64, travel through the microporous separator material comprised of the electrically insulating separator layer 43, and enter the negative electrode active material layer 49 at the outer surfaces 61, 63. Depending on the negative electrode active material used, the lithium ions (or other carrier ions) may be intercalated (e.g., located without forming an alloy within the matrix of the negative electrode active material) or may form an alloy. Concurrent with the movement of lithium ions (or other carrier ions) between the positive and negative electrodes, the negative electrode current collector layer 47 and the positive electrode current collector layer 48 transmit electrons between the respective negative electrode bus 23 and positive electrode bus 24 (see FIG. 2). The negative electrode bus 23 and the positive electrode bus 24 are electrically connected to the negative and positive terminals of an energy storage device (not shown) comprising the electrode structure 20, or to an external energy supply (not shown), or to an external energy consumer (not shown).

[0065] The anode backbone 51 provides mechanical stability for the anode active material layer 49. In general, the anode backbone 51 may comprise any material that can be shaped, such as metals, semiconductors, organics, ceramics, and glasses. Presently preferred materials include semiconductor materials such as silicon and germanium. However, the anode backbone may alternatively incorporate carbon-based organics or metals such as aluminum, copper, nickel, cobalt, titanium, and tungsten. In one exemplary embodiment, the anode backbone 51 comprises silicon. For example, the silicon may be monocrystalline silicon, polycrystalline silicon, amorphous silicon, or combinations thereof.

[0066] Depending on the application, the anode backbone 51 may be conductive or insulating. For example, in some embodiments, the anode backbone 51 has a conductivity of less than 10 Siemens / cm. By way of further example, in some embodiments, the anode backbone 51 has a conductivity of less than 1 Siemens / cm. By way of further example, in some embodiments, the anode backbone 51 has a conductivity of less than 10 Siemens / cm. -1 In other embodiments, the anode backbone 51 may have a conductivity of at least 10 Siemens / cm. By way of further example, in some embodiments, the anode backbone 51 may have a conductivity of at least 10 Siemens / cm. 2 By way of further example, in some embodiments, the negative electrode backbone 51 may have a conductivity of at least 10 3 It may have a conductivity in Siemens / cm.

[0067] The negative electrode current collector layer 47 is typically at least about 10 3 For example, in one such embodiment, the negative electrode current collector layer 47 has a conductivity of at least about 10 4 By way of further example, the negative electrode current collector layer 47 in one such embodiment has a conductivity of at least about 10 5It has a conductivity of siemens / cm. In general, the negative electrode current collector layer 47 may include any metal or other conductor conventionally used as a current collector material for a negative electrode, such as carbon, cobalt, chromium, copper, nickel, titanium, or alloys of one or more of these. The negative electrode current collector 47 may be fabricated by processes such as electrodeposition, electroless deposition, immersion deposition, physical vapor deposition, chemical vapor deposition, and the like.

[0068] The thickness of the negative electrode current collector layer 47 in this embodiment (i.e., the shortest distance between the negative electrode backbone and the negative electrode active material layer) depends on the composition of the layers and the performance specifications of the electrochemical stack, but generally, the thickness ranges from about 1 micrometer to about 100 micrometers.

[0069] The anode active material layer 49 may include an anode active material capable of absorbing and releasing carrier ions, such as lithium ions, sodium ions, potassium ions, calcium ions, or magnesium ions. Such materials include carbon-based materials, such as graphite and soft or hard carbon, or any of a wide range of metals, metalloids, alloys, oxides, and compounds capable of forming an alloy with lithium. Specific examples of metals or metalloids that may constitute the anode material include tin, lead, magnesium, aluminum, boron, gallium, silicon, indium, zirconium, germanium, bismuth, cadmium, antimony, silver, zinc, arsenic, hafnium, yttrium, and palladium. In an exemplary embodiment, the anode active material layer 49 includes aluminum, tin, or silicon, or oxides thereof, nitrides thereof, fluorides thereof, or other alloys thereof. In another exemplary embodiment, the anode active material layer 49 includes silicon or an alloy thereof. In each of the embodiments and examples described in this paragraph, the anode active material layer 49 may be a particle aggregate electrode or a monolithic electrode.

[0070] The positive electrode backbone 52 provides mechanical stability for the positive electrode active material layer 50. In general, the positive electrode backbone 52 may comprise any material that can be shaped, such as metals, semiconductors, organics, ceramics, and glasses. Presently preferred materials include semiconductor materials such as silicon and germanium. However, the positive electrode backbone may alternatively incorporate carbon-based organics or metals such as aluminum, copper, nickel, cobalt, titanium, and tungsten. In one exemplary embodiment, the positive electrode backbone 52 comprises silicon. For example, the silicon may be monocrystalline silicon, polycrystalline silicon, amorphous silicon, or combinations thereof.

[0071] Depending on the application, the positive electrode backbone 52 may be conductive or insulating. For example, in some embodiments, the positive electrode backbone 52 has a conductivity of less than 10 Siemens / cm. By way of further example, in some embodiments, the positive electrode backbone 52 has a conductivity of less than 1 Siemens / cm. By way of further example, in some embodiments, the positive electrode backbone 52 has a conductivity of less than 10 Siemens / cm. -1 In other embodiments, the positive electrode backbone 52 may have a conductivity of at least 10 Siemens / cm. By way of further example, in some embodiments, the positive electrode backbone 52 may have a conductivity of at least 10 Siemens / cm. 2 By way of further example, in some embodiments, the positive electrode backbone 52 may have a conductivity of at least 10 3 It may have a conductivity in Siemens / cm.

[0072] In the embodiment shown in FIG. 3, the positive electrode current collector layer 48 is located between the positive electrode backbone 52 and the positive electrode active material layer 50, and is typically at least about 10 3 For example, in one such embodiment, the positive electrode current collector layer 48 has a conductivity of at least about 10 4 By way of further example, the positive electrode current collector layer 48 in one such embodiment has a conductivity of at least about 10 5The positive current collector 48 has a conductivity of siemens / cm. The positive current collector 48 may include any of the metals previously identified with respect to the negative current collector, for example, in some embodiments the positive current collector 48 includes aluminum, carbon, chromium, gold, nickel, NiP, palladium, platinum, rhodium, ruthenium, an alloy of silicon and nickel, titanium, or combinations thereof (see Non-Patent Document 3). As a further example, in some embodiments the positive current collector 48 includes gold or an alloy thereof, such as gold silicide. As a further example, in some embodiments the positive current collector 48 includes nickel or an alloy thereof, such as nickel silicide. The positive current collector 48 may be fabricated by processes such as electrodeposition, electroless deposition, immersion deposition, physical vapor deposition, chemical vapor deposition, and the like. The positive and negative current collectors may be fabricated simultaneously or sequentially using known patterning and metal deposition techniques.

[0073] The positive electrode active material layer 50 may include any of a wide variety of cathode active materials, including mixtures of cathode active materials. For example, in the case of a lithium-ion battery, the positive electrode active material layer 50 may include a cathode material selected from transition metal oxides, transition metal sulfides, transition metal nitrides, lithium-transition metal oxides, lithium-transition metal sulfides, and lithium-transition metal nitrides that may be used alternatively. The transition metal elements of these transition metal oxides, transition metal sulfides, and transition metal nitrides may include metal elements having a d-shell or an f-shell. Specific examples of such metal elements are Sc, Y, lanthanides, actinides, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pb, Pt, Cu, Ag, and Au. Additional cathode active materials include LiCoO 2 , LiNi 0.5 Mn 1.5 O 4 , Li(Ni x Co y Al 2 )O 2 , LiFePO 4 , Li 2 MnO 4 , V 2 O 5, molybdenum oxysulfide, and combinations thereof. The positive electrode active material layer may be deposited to form the positive electrode structure by any of a wide range of techniques including, for example, electrophoretic deposition, electrodeposition, co-evaporation, or slurry deposition. In one exemplary embodiment, one of the above positive electrode active materials or combinations thereof is electrophoretically deposited in particulate form. In another exemplary embodiment, V 2 O 5 In another exemplary embodiment, one of the above-mentioned positive electrode active materials or a combination thereof is co-deposited (co-deposited) in a particulate form within a conductive matrix such as polyaniline. In another exemplary embodiment, one of the above-mentioned positive electrode active materials or a combination thereof is slurry deposited (deposited) in a particulate form.

[0074] The negative electrode backbone 51 and the positive electrode backbone 52 may be fabricated by any method known in the art for fabricating three-dimensional structures. For example, the silicon backbone for the positive electrode (cathode) and the silicon backbone for the negative electrode (anode) may be fabricated simultaneously with a wafer that is bonded to a base with a temporary, permanent or semi-permanent adhesive. Non-exhaustive methods for bonding the base to the wafer include gluing with inorganic or organic adhesives, anodic oxidation bonding, pressure bonding, thermal bonding, etc. Silicon-on-insulator wafers, anodic glass bonded wafers, and wafers with temporary carriers are examples of bases that are bonded onto active substrates. The wafer can then be patterned and silicon can be removed at unwanted sites, leaving structures that can function as electrode backbones. In some embodiments, the backbone may be fabricated in a passive manner by removing material at unwanted sites from a planar substrate by laser machining, electrical discharge machining, precision machining, ablation and drilling. In other embodiments, each backbone can be fabricated individually or separately in a proactive manner by building up layers using methods such as 3D printing, stencil printing and lamination, gravure printing, injection molding, pressing and sintering, gel casting and sintering, slurry casting, tape casting, whether using sintering, microforming, electroforming, or others. Other exemplary processes that can be used to fabricate the backbone include growing posts, rods, corrugations, etc. using vacuum-based deposition (evaporation) processes such as sputtering through a mask, evaporation, etc. Yet another exemplary manufacturing method includes growing nanowires or nanostructures on a patterned base material.

[0075] The negative electrode active material layer 49 may be formed or otherwise assembled using methods such as electrodeposition, electrophoretic deposition, vapor deposition, catalyst-based growth such as vapor-liquid-solid deposition, gel casting, tape casting, patterning, and slurry deposition, followed by densification by sintering, bonding, curing, and the like. In some embodiments, the negative electrode material layer and the negative electrode backbone may comprise the same material such as silicon, aluminum, tin, and the negative electrode material layer and the negative electrode backbone may be fabricated simultaneously. Similarly, the positive electrode active material layer 50 may be formed or otherwise assembled using methods such as electrodeposition, electrophoretic deposition, vapor deposition, catalyst-based growth such as vapor-liquid-solid deposition, gel casting, tape casting, patterning, and slurry deposition, followed by densification by pressing, sintering, bonding, curing, and the like.

[0076] In some embodiments, the negative electrode active material layer 49 is microstructured to provide a void volume fraction sufficient to accommodate the volume expansion and contraction of lithium ions (or other carrier ions) as they are incorporated into or exit the negative electrode active material layer 49 during the charge and discharge process. In general, the void volume fraction of the negative electrode active material layer is at least 0.1. Typically, however, the void volume fraction of the negative electrode active material layer is 0.8 or less. For example, the void volume fraction of the negative electrode active material layer in some embodiments is from about 0.15 to about 0.75. As a further example, the void volume fraction of the negative electrode active material layer in some embodiments is from about 0.2 to about 0.7. As a further example, the void volume fraction of the negative electrode active material layer in some embodiments is from about 0.25 to about 0.6.

[0077] Depending on the composition of the microstructured negative electrode active material layer and the method of its formation, the microstructured negative electrode active material layer may comprise a macroporous, microporous or mesoporous material layer, or a combination thereof, such as a combination of microporosity and mesoporosity, or a combination of mesoporosity and macroporosity. Microporous materials are typically characterized by pore sizes of less than 10 nm, wall sizes of less than 10 nm, pore depths of 1-50 micrometers, and a pore morphology that is generally characterized by a "spongy" appearance, irregular walls and branched pores. Mesoporous materials are typically characterized by pore sizes of 10-50 nm, wall sizes of 10-50 nm, pore depths of 1-100 micrometers, and a pore morphology that is generally characterized by relatively well-defined branched or tree-like pores. Macroporous materials are typically characterized by pore sizes greater than 50 nm, wall sizes greater than 50 nm, pore depths of 1-500 micrometers, and pore morphologies that may be variable, linear, branched, or dendritic, and smooth-walled, or rough. Furthermore, the void volume may include open or closed voids, or a combination thereof. In some embodiments, the void volume includes open voids, i.e., the negative electrode active material layer includes voids at the outer surface of the negative electrode active material layer (i.e., the surface facing the separator and the positive electrode active material layer) that have openings through which lithium ions (or other carrier ions) can pass on their way to and from the negative electrode active material layer, e.g., lithium ions may enter the negative electrode active material layer through the void openings after leaving the positive electrode active material layer. In another embodiment, the void volume includes closed voids, i.e., the negative electrode active material layer includes voids that are surrounded by the negative electrode active material. Generally, open and closed voids each provide room for the negative electrode active material layer to expand upon the ingress of carrier ions, but open voids can provide a larger interfacial surface area for the carrier ions, whereas closed voids tend to be less susceptible to the solid electrolyte interface ("SEI"). Thus, in certain embodiments, it is preferred that the negative electrode active material layer includes a combination of open and closed voids.

[0078] In some embodiments, the negative electrode active material layer 49 comprises porous aluminum, tin, or silicon, or an alloy thereof. The porous silicon layer may be formed, for example, by anodization, by etching (e.g., depositing a noble metal, such as gold, platinum, silver, or gold / palladium, onto the (100) surface of single crystal silicon and etching the surface with a mixture of hydrofluoric acid and hydrogen peroxide), or by other methods known in the art, such as patterned chemical etching. Furthermore, the porous negative electrode active material layer generally has a porosity of at least about 0.1 and less than 0.8, and a thickness of about 1 micrometer to about 100 micrometers. For example, in some embodiments, the negative electrode active material layer 49 comprises porous silicon, has a thickness of about 5 micrometers to about 100 micrometers, and has a porosity of about 0.15 to about 0.75. By way of further example, anode active material layer 49 in one embodiment comprises porous silicon, has a thickness of about 10 micrometers to about 80 micrometers, and has a porosity of about 0.15 to about 0.7. By way of further example, anode active material layer 49 in one such embodiment comprises porous silicon, has a thickness of about 20 micrometers to about 50 micrometers, and has a porosity of about 0.25 to about 0.6. By way of further example, anode active material layer 49 in one embodiment comprises a porous silicon alloy (such as nickel silicide), has a thickness of about 5 micrometers to about 100 micrometers, and has a porosity of about 0.15 to about 0.75.

[0079] In another embodiment, the negative electrode active material layer 49 comprises aluminum, tin or silicon fibers, or alloys thereof. The individual fibers may have a diameter (thickness dimension) of about 5 nm to about 10,000 nm, and a length that generally corresponds to the thickness of the negative electrode active material layer 49. The silicon fibers (nanowires) may be formed, for example, by chemical vapor deposition, such as vapor-liquid-solid (VLS) growth and solid-liquid-solid (SLS) growth, or other techniques known in the art. Furthermore, the negative electrode active material layer 49 generally has a porosity of at least about 0.1 and less than 0.8, and a thickness of about 1 micrometer to about 200 micrometers. For example, the negative electrode active material layer 49 in one embodiment comprises silicon nanowires, has a thickness of about 5 micrometers to about 100 micrometers, and has a porosity of about 0.15 to about 0.75. By way of further example, the anode active material layer 49 in one embodiment comprises silicon nanowires, has a thickness of about 10 micrometers to about 80 micrometers, and has a porosity of about 0.15 to about 0.7. By way of further example, the anode active material layer 49 in one such embodiment comprises silicon nanowires, has a thickness of about 20 micrometers to about 50 micrometers, and has a porosity of about 0.25 to about 0.6. By way of further example, the anode active material layer 49 in one embodiment comprises silicon alloy (such as nickel silicide) nanowires, has a thickness of about 5 micrometers to about 100 micrometers, and has a porosity of about 0.15 to about 0.75.

[0080] Although there can be considerable variation from fiber to fiber, the aluminum, tin or silicon (or alloys thereof) nanowires have a major axis (sometimes referred to as the central axis) that is largely perpendicular to the negative electrode backbone 51 (at the point of attachment of the nanowire to the negative electrode active material layer).

[0081] In another embodiment, the negative electrode active material layer 49 includes nanowires of silicon or its alloys and porous silicon or its alloys. In such embodiments, the negative electrode active material layer generally has a porosity of at least about 0.1 and less than 0.8, as described above for porous silicon and silicon nanowires, and a thickness of from about 1 micrometer to about 100 micrometers.

[0082] 4, each element 21 of the negative electrode population extends from an inner surface 27 of the negative electrode bus 23, and each element 22 of the positive electrode population extends from an inner surface 28 of the positive electrode bus 24, with the inner surfaces 27, 28 facing or opposing each other. The negative electrode bus 23 includes conductive material that electrically connects each element 21 of the negative electrode population to other elements of the negative electrode population. Similarly, the positive electrode bus 24 includes conductive material that electrically connects each element 22 of the positive electrode population to each other. For ease of illustration, electrically insulating separator material layer 43 (see FIGS. 2 and 3) is not shown.

[0083] Referring now to FIG. 5, each element 21 of the negative electrode population has a bottom 31 proximal to the inner surface 27 of the negative electrode bus 23, a top 33 distal from the inner surface 27, and a width W NE and length L NE and longitudinal axis A NE and the length L NE corresponds to the distance between the bottom 31 and the top 33, and the longitudinal axis A NE 2, from the inner surface 27 in a direction that is generally perpendicular to the direction D. In the context of the XYZ coordinate system illustrated in FIG. NE is measured along the "X" axis (and perpendicular to direction D).

[0084] Next, referring to FIG. 7, each element 21 of the negative electrode group has a width W NE and height H NE And the outer circumference P NE and has a width W NE and height H NE are mutually exclusive and of length L NE In this embodiment, the perimeter P NE is 2W NE +2HNE The width W NE and height H NE will vary depending on the energy storage device and its intended use, but in many embodiments, W NE The value of is in the range of about 0.01 mm to 2.5 mm, and H NE The value of W may range from about 0.05 mm to 10 mm. For example, in one embodiment, NE In one embodiment, W may range from about 0.025 mm to about 2 mm. NE In one embodiment, H may range from about 0.05 mm to about 1 mm. NE In one embodiment, H may range from about 0.05 mm to about 5 mm. NE Generally, L ranges from about 0.05 mm to about 1 mm. NE (See Figure 5) is W NE and H NE For example, in one embodiment, L NE and W NE and H NE and each of L NE and W NE The ratio of L to L is at least 5:1, NE and H NE (The ratio of L to L is at least 5:1.) NE and W NE and H NE and each of the L is at least 10:1. NE and W NE and H NE and each of the L is at least 15:1. NE and W NE and H NE and each of the L is at least 20:1. NE is the outer circumference P NEIt is preferable that the L NE and P NE and L are each at least 1.25:1. NE and P NE and L are each at least 2.5:1. NE and P NE and H are each at least 3.75:1. NE and W NE and H are typically at least 0.4:1, respectively. For example, in one embodiment, NE and W NE and H NE and W NE and H NE and W NE The ratio of H to H is at least 20:1. NE and W NE The ratio of H to H is generally less than 1,000:1. NE and W NE and H in one embodiment are each less than 500:1. NE and W NE and H in one embodiment are each less than 100:1. NE and W NE and H in one embodiment are each less than 10:1. NE and W NE The ratio of length L to length Y is in the range of about 2:1 to about 100:1, respectively. In the context of the XYZ coordinate system illustrated in FIG. NE is measured along the "X" axis (and perpendicular to direction D), and W NE is measured along the "Y" axis, and H NE is measured along the "Z" axis.

[0085] Typically, the negative electrode backbone 51 has a width W of the negative electrode. NE 7. The thickness of the anode backbone 51 can be substantially thicker, but typically will not exceed 100 micrometers in thickness. Greater thicknesses are possible, but may adversely affect energy density. For example, in some embodiments, the anode backbone 51 has a thickness of from about 1 micrometer to about 50 micrometers. Generally, the anode backbone 51 has a thickness of from about 1 micrometer to about 50 micrometers (anode height H NE and a height H of at least about 50 micrometers, more typically at least about 100 micrometers (measured in the same direction as the NB In general, however, the anode backbone 51 typically has a height of about 10,000 micrometers or less, and more typically about 5,000 micrometers or less. By way of example, in some embodiments, the anode backbone 51 has a thickness of about 5 micrometers to about 50 micrometers and a height of about 50 micrometers to about 5,000 micrometers. By way of further example, in some embodiments, the anode backbone 51 has a thickness of about 5 micrometers to about 20 micrometers and a height of about 100 micrometers to about 1,000 micrometers. By way of further example, in some embodiments, the anode backbone 51 has a thickness of about 5 micrometers to about 20 micrometers and a height of about 100 micrometers to about 2,000 micrometers.

[0086] The negative electrode active material layer 49 has a thickness of at least 1 micrometer (e.g., the width W of the negative electrode). NE3 ) (the shortest distance between the current collector layer 47 and the electrically insulating separator layer 43 as shown in FIG. 3 when measured in the same direction as the negative electrode height H 1 as shown in FIG. 5 ). In general, however, the negative electrode active material layer 49 typically has a thickness not exceeding 200 micrometers. For example, in some embodiments, the negative electrode active material layer 49 has a thickness from about 1 micrometer to about 100 micrometers. As a further example, in some embodiments, the negative electrode active material layer 49 has a thickness from about 2 micrometers to about 75 micrometers. As a further example, in some embodiments, the negative electrode active material layer 49 has a thickness from about 10 micrometers to about 100 micrometers. As a further example, in some embodiments, the negative electrode active material layer 49 has a thickness from about 5 micrometers to about 50 micrometers. Additionally, the negative electrode active material layer 49 on each outer surface of the negative electrode backbone 51 is preferably at least 100 micrometers thick (the shortest distance between the current collector layer 47 and the electrically insulating separator layer 43 as shown in FIG. 5 ). NE) and has a height of at least about 50 micrometers, more typically at least about 100 micrometers. In general, however, the negative electrode active material layer 49 typically has a height of no more than about 10,000 micrometers, and more typically no more than about 7,500 micrometers. By way of example, in some embodiments, the negative electrode active material layer 49 has a thickness of about 1 micrometer to about 200 micrometers and a height of about 50 micrometers to about 7,500 micrometers. By way of further example, the negative electrode active material layer 49 in some embodiments has a thickness of about 1 micrometer to about 50 micrometers and a height of about 100 micrometers to about 1,000 micrometers. By way of further example, the negative electrode active material layer 49 in some embodiments has a thickness of about 5 micrometers to about 20 micrometers and a height of about 100 micrometers to about 1,000 micrometers. By way of further example, negative electrode active material layer 49 in some embodiments has a thickness of about 10 micrometers to about 100 micrometers and a height of about 100 micrometers to about 1,000 micrometers. By way of further example, negative electrode active material layer 49 in some embodiments has a thickness of about 5 micrometers to about 50 micrometers and a height of about 100 micrometers to about 1,000 micrometers.

[0087] 6, each element 22 of the positive electrode population has a bottom 32 proximate the inner surface 28 of the positive electrode bus 24, a top 34 distal from the positive electrode substrate surface 26, and a width W PE and length L PE and longitudinal axis A PE and the length L PE corresponds to the distance between the bottom 32 and the top 34, and the longitudinal axis A PE 2, from the inner surface 28 along a direction that is generally perpendicular to the direction D. In the context of the XYZ coordinate system illustrated in FIG. PE is measured along the "X" axis (and perpendicular to direction D).

[0088] Referring now to FIG. 8, each element 22 of the positive electrode group has a width W PE and height H PE And the outer circumference P PE and has a width W PE and height H PE are mutually exclusive and of length L PE In this embodiment, the perimeter P PE is 2W PE +2H PE The width W PE and height H PE will vary depending on the energy storage device and its intended use, but in many embodiments, W PE is in the range of about 0.01 mm to 2.5 mm, and H PE The value of W may range from about 0.05 mm to 10 mm. For example, in one embodiment, PE In one embodiment, W may range from about 0.025 mm to about 2 mm. PE In one embodiment, H may range from about 0.05 mm to about 1 mm. PE In one embodiment, H may range from about 0.05 mm to about 5 mm. PE Generally, L ranges from about 0.05 mm to about 1 mm. PE (See Figure 6) is W PE and H PE For example, in one embodiment, L PE and W PE and H PE and each of the L PE and W PE and L are at least 5:1, respectively. PE and H PE and the ratio of L to L is at least 5:1, respectively. PE and W PE and H PE and each of the L is at least 10:1. PEand W PE and H PE and each of the L is at least 15:1. PE and W PE and H PE and each of the L is at least 20:1. PE is the outer circumference P PE It is preferable that the L PE and P PE and L are each at least 1.25:1. PE and P PE and L are each at least 2.5:1. PE and P PE and H are each at least 3.75:1. PE and W PE and H are typically at least 0.4:1, respectively. For example, in one embodiment, PE and W PE and H PE and W PE and H PE and W PE The ratio of H to H is at least 20:1. PE and W PE The ratio of H to H is generally less than 1,000:1. PE and W PE and H in one embodiment are each less than 500:1. PE and W PE and H in one embodiment are each less than 100:1. PE and W PE and H in one embodiment are each less than 10:1. PE and W PEIn the context of the XYZ coordinate system illustrated in FIG. PE is measured along the "X" axis (and perpendicular to direction D), and W PE is measured along the "Y" axis, and H PE is measured along the "Z" axis.

[0089] Typically, the positive electrode backbone 52 has a width W of the positive electrode. PE 8. The thickness of the positive electrode backbone 52 can be substantially thicker, but generally will not exceed 100 micrometers in thickness. For example, in one embodiment, the positive electrode backbone 52 has a thickness of from about 1 micrometer to about 50 micrometers. Generally, the positive electrode backbone 52 has a thickness of at least 1 micrometer when measured in the same direction as the negative electrode height H NE and a height H of at least about 50 micrometers, more typically at least about 100 micrometers (measured in the same direction as the PE In general, however, the positive electrode backbone 52 typically has a height of about 10,000 micrometers or less, and more typically about 5,000 micrometers or less. By way of example, in some embodiments, the positive electrode backbone 52 has a thickness of about 5 micrometers to about 50 micrometers and a height of about 50 micrometers to about 5,000 micrometers. By way of further example, in some embodiments, the positive electrode backbone 52 has a thickness of about 5 micrometers to about 20 micrometers and a height of about 100 micrometers to about 1,000 micrometers. By way of further example, in some embodiments, the positive electrode backbone 52 has a thickness of about 5 micrometers to about 20 micrometers and a height of about 100 micrometers to about 2,000 micrometers.

[0090] The positive electrode active material layer 50 has a thickness of at least 1 micrometer (e.g., the width W of the positive electrode). PE3 ) (the shortest distance between the current collector layer 48 and the electrically insulating separator layer 43 as shown in FIG. 3 when measured in the same direction as the positive electrode height H 1 as shown in FIG. 6 ). In general, however, the positive electrode active material layer 50 typically has a thickness not exceeding 500 micrometers. For example, in some embodiments, the positive electrode active material layer 50 has a thickness of about 1 micrometer to about 200 micrometers. As a further example, in some embodiments, the positive electrode active material layer 50 has a thickness of about 2 micrometers to about 100 micrometers. As a further example, in some embodiments, the positive electrode active material layer 50 has a thickness of about 10 micrometers to about 100 micrometers. As a further example, in some embodiments, the positive electrode active material layer 50 has a thickness of about 5 micrometers to about 50 micrometers. Additionally, the positive electrode active material layer 50 on each outer surface of the positive electrode backbone 51 is preferably at least 100 micrometers thick (the positive electrode height H 1 as shown in FIG. 6 ). PE) and has a height of at least about 50 micrometers, more typically at least about 100 micrometers. In general, however, the positive electrode active material layer 50 typically has a height of about 10,000 micrometers or less, and more typically about 7,500 micrometers or less. By way of example, in some embodiments, the positive electrode active material layer 50 has a thickness of about 1 micrometer to about 200 micrometers and a height of about 50 micrometers to about 7,500 micrometers. By way of further example, the positive electrode active material layer 50 in some embodiments has a thickness of about 1 micrometer to about 50 micrometers and a height of about 100 micrometers to about 1,000 micrometers. By way of further example, the positive electrode active material layer 50 in some embodiments has a thickness of about 5 micrometers to about 20 micrometers and a height of about 100 micrometers to about 1,000 micrometers. By way of further example, in some embodiments, positive electrode active material layer 50 has a thickness from about 10 micrometers to about 100 micrometers and a height from about 100 micrometers to about 1,000 micrometers. By way of further example, positive electrode active material layer 50 in some embodiments has a thickness from about 5 micrometers to about 50 micrometers and a height from about 100 micrometers to about 1,000 micrometers.

[0091] 9, in one embodiment, electrically insulating separator layer 43 extends from surface 28 of positive bus 24 to surface 27 of negative bus 23 and is aligned along each axis A of elements 22 and 21. PE and A NE The length L of element 22 and element 21 PE and L NE In one such embodiment, electrically insulating separator layer 43 includes a microporous separator material (as described above), which is oriented along each axis A of element 22 and element 21. PE and A NE The length L of element 22 and element 21 PE and LNE The electrically insulating material layer 43 also includes microporous separator material in the region between the top 33 of the negative electrode 21 and the surface 28 of the positive electrode bus 24 (as described above). Thus, in this embodiment, the electrically insulating material layer 43 surrounds each element 21 of the negative electrode population and each element 22 of the positive electrode population. In other words, in this embodiment, the electrically insulating separator layer 43 (i) surrounds the entire length L of each element 21 of the negative electrode population NE The longitudinal axis A of each element 21 extends NE and (ii) the overall length L of each element 22 of the positive electrode group. PE The longitudinal axis A of each element 22 extends PEと、 It surrounds the upper portion 34 of each element 22 of the positive electrode group.

[0092] 10, in one embodiment, a three-dimensional battery 70 of the present invention comprises a battery housing 72, an electrode stack 74, and negative and positive tabs 41, 42 for electrically connecting the electrode stack 74 to an external energy supply or consumer (not shown). The electrode stack 74 comprises six layers of electrode structures 20 (see FIG. 2), which are stacked in a direction perpendicular to the direction of progression of the stacking of a series of interdigitated electrodes within each electrode structure 20. Referring again to FIG. 2, the stacking direction of the six layers of electrode structures in this embodiment is the "Z" direction of the XYZ coordinate system shown in FIG. 2, and perpendicular to the direction D. The number of electrode structures in the electrode stack 74 is not critical and may range, for example, from 1 to 50, but typically there are between 2 and 20 electrode structures in the electrode stack. After filling the battery housing with non-aqueous electrolyte, the battery housing 72 may be sealed by folding the lid 72A at hinge 72B and gluing the lid 72A to the top surface 72C.

[0093] In one embodiment, the negative electrode tab extension 25 is electrically connected (e.g., using conductive glue) to the negative electrode bus 23 of each electrode structure 20 in the stack 74, and the positive electrode tab extension 26 is electrically connected (e.g., using conductive glue) to the positive electrode bus 24 of each electrode structure 20 in the stack 74. As shown, the negative electrode tab extension 25 is electrically connected to the negative electrode bus 23 of each of the six electrode structures 20, and the positive electrode tab extension 26 is electrically connected to the positive electrode bus 24; in other embodiments, the negative and positive electrode tab extensions 25, 26 may be electrically connected to a greater or lesser number of negative and positive electrode buses in the electrode stack 74, and the number of electrode structures may range, for example, from 1 to 50, but typically ranges from 2 to 20. In an alternative embodiment, stack 74 may include two or more negative electrode tab extensions 25 and two or more positive electrode tab extensions 26, regardless of the number of electrode structures in the stack.

[0094] The anode tab 41 and anode tab extension 25, and the cathode tab 42 and cathode tab extension 42 may comprise any of a wide variety of conductive materials. For example, in some embodiments, the anode tab 41 and anode tab extension 25, and the cathode tab 42 and cathode tab extension 42, independently, comprise a conductive material such as silicon, carbon, carbon composites, metal silicides, etc. Exemplary materials for the positive tab and positive tab extension include the same materials identified for the positive bus, and exemplary materials for the negative tab and negative tab extension include the same materials identified for the negative bus.

[0095] The anode tab 41, anode tab extension 25, cathode tab 42, and cathode tab extension 26 may be attached to the anode bus 23 and cathode bus 24, respectively, by a wide variety of techniques. Methods for attaching the tabs, tab extensions, and buses may include gluing, soldering, adhesives, sintering, crimping, brazing, spray bonding, clamping, or combinations thereof. Adhesion may include joining materials with conductive materials such as conductive epoxies, conductive elastomers, and mixtures of insulating organic adhesives filled with conductive metals such as nickel-filled epoxies, carbon-filled epoxies, and others. Conductive pastes may be used to join the materials, and bond strength may be adjusted by temperature (sintering), light (UV curing, cross-linking), or chemical curing (catalyst-based cross-linking). Adhesion processes may include wire bonding, ribbon bonding, ultrasonic bonding, and welding processes may include ultrasonic welding, resistance welding, laser beam welding, electron beam welding, induction welding, and cold welding. Bonding of these materials can also be performed by bonding the materials together using coating processes such as thermal spray coatings such as plasma spray, flame spray, arc spray, etc. As an example, a nickel or copper mesh can be bonded onto a nickel bath using nickel spray as an adhesive.

[0096] 11, the battery housing 72 may be filled with non-aqueous electrolyte (not shown) and the lid 72A folded over and sealed on top (see FIG. 10) to enclose the electrode stack 74. Tabs 41, 42 extend from the sealed housing in a direction perpendicular to the stacking direction of the individual electrode structures 20 in the electrode stack 74 and parallel to the progression of the series of interdigitated electrodes in each electrode structure 20 in the electrode stack 74 to allow connection to an energy supply or consumer (not shown).

[0097] In certain embodiments, the battery housing may include two or more electrode structures (sometimes referred to as dies) stacked vertically, parallel, or vertically and horizontally with respect to each other, and a tab extension is connected to each electrode to provide an electrical connection to the environment outside the battery. When the dies are stacked vertically, the bottoms of the negative electrodes (or negative electrode buses, whichever exists) in the different electrode structures are aligned vertically with each other, and the bottoms of the positive electrodes (or positive electrode buses, whichever exists) in the different electrode structures are aligned vertically with each other. In certain embodiments, each electrode structure in the stack has a top and bottom coating of separator material, as shown in FIG. 2. However, in other embodiments, the top coating, bottom coating, or top and bottom coatings of separator material may be omitted, and a separate separator layer may be inserted between the electrode structures (dies) to provide electrical insulation. For this purpose, commercially available battery separators may be cut to the desired size and used. When the dies are stacked, in some embodiments, the tab extensions of the positive and negative electrodes in the electrode structure are electrically connected to the ends of the electrode buses (if present) or the electrode ends of their respective groups by gluing, plasma spraying, welding, etc. Depending on the intended application, each tab extension may be connected to an individual electrode structure (die) in the electrode stack. Alternatively, a single tab extension may be electrically connected to more than one electrode structure (die) in the stack, in one such embodiment the tab extension runs the height of the stack (see, e.g., 26 in FIG. 10) and makes electrical connection to all of the electrode structures (dies) in the stack.

[0098] Instead of stacking the dies vertically one above the other, in some embodiments, the dies are aligned adjacent to each other in the X-plane. The alignment can occur along only one axis (e.g., only the X-axis) or along both axes. In one such embodiment, the polarity of the electrode buses on each die is alternately reversed such that the cathode bus from one die is adjacent to the cathode bus from the next die and the anode bus from one die is next to the anode bus of the next die. In this manner, a common tab can be used to connect two adjacent dies, saving weight and volume. When aligned in the XY plane, it may be necessary to link multiple anode and / or cathode tabs together to form a single anode connection and a single cathode connection. This can be accomplished either inside or outside the battery housing. In certain embodiments, the multiple anode and / or multiple cathode tabs may emerge from the battery housing unlinked. Alternatively, a single anode and cathode connection may be brought out to the outside of the battery housing. In this embodiment, the cathode tab is initially formed into a T-shape. The top of the T connects to two adjacent cathode buses. The bottom of the T is bent 90 degrees to extend along the bottom of the aligned dies. The bottoms of the cathode tabs are one above the other along the bottom of the aligned dies. The tabs are then electrically connected to each other by resistance welding, laser welding, spot welding, or connected with a conductive adhesive. Then, only one of the cathode tabs is pulled out of the battery housing. Similarly, the anode tabs are initially formed into a T shape. The top of the T connects to two adjacent anode buses. The bottom of the T is bent 90 degrees to extend along the bottom of the aligned dies. The bottoms of the anode tabs are one above the other along the bottom of the aligned dies. The tabs are then electrically connected to each other by resistance welding, laser welding, spot welding, or connected with a conductive adhesive. Then, only one of the anode tabs is pulled out of the battery housing. Alignment in the XY plane can also be combined with stacking of dies in the Z plane. In this way, batteries much larger than the individual dies can be produced.

[0099] In the case of lithium ion batteries in portable electronic devices such as cell phones and computers, for example, battery housing 72 may be replaced with a pouch or other conventional battery housing.

[0100] 12, in one alternative embodiment, an electrically insulating separator layer 43 is disposed on each element 21 of the negative electrode population along axis A. NE The electrically insulating separator layer 43 in this embodiment is between adjacent pairs of negative and positive electrode elements 21 and 22, but is aligned with the axis A of each element 22 of the positive electrode population. PE The electrically insulating separator layer 43 includes a microporous separator material (as described above) between the opposing outer surfaces 61, 62 of each element 21, 22 and between the opposing outer surfaces 63, 64 of each element 21, 22. For example, in one such embodiment, the electrically insulating separator layer 43 includes a microporous separator material (as described above), and the microporous separator material is disposed about the axis A of each element 21. NE The length L of each element 21 NE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 21. NE The length L of each element 21 NE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 21. NE The length L of each element 21 NE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 21. NE The length L of each element 21 NEBy way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 21. NE The length L of each element 21 NE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 21. NE The length L of each element 21 NE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 21. NE The length L of each element 21 NE In each of the exemplary embodiments described above, electrically insulating separator layer 43 also includes microporous separator material (as described above) in areas surrounding front surface 65 and back surface 67 of element 21.

[0101] 13, in one alternative embodiment, the height H of each element 21 of the negative electrode population NE is the height H of each element 22 of the positive electrode group PE In this embodiment, and as will be more fully described in connection with FIG. 12, the electrically insulating separator layer 43 is aligned with the axis A of each element 21 of the negative electrode population. NE The length L of each element 21 of the negative electrode group NE The electrically insulating separator layer 43 also includes microporous separator material (as described above) in areas surrounding the front surface 65 and back surface 67 of the element 21.

[0102] 14, in one alternative embodiment, an electrically insulating separator layer 43 is disposed between the axis A of each element 22 of the positive electrode population. PE The electrically insulating separator layers 43 in this embodiment are present between adjacent pairs of negative electrode elements 21 and positive electrode elements 22, but are spaced apart from the axis A of each element 21 of the negative electrode population. NE The electrically insulating separator layer 43 includes a microporous separator material (as described above) between the opposing outer surfaces 61, 62 of each element 21, 22 and between the opposing outer surfaces 63, 64 of each element 21, 22. For example, in one such embodiment, the electrically insulating separator layer 43 includes a microporous separator material (as described above), and the microporous separator material is disposed about the axis A of each element 22. PE The length L of each element 22 PE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 22. PE The length L of each element 22 PE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 22. PE The length L of each element 22 PE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 22. PE The length L of each element 22 PE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 22. PE The length L of each element 22 PEBy way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 22. PE The length L of each element 22 PE By way of further example, the electrically insulating separator layer 43 in one such embodiment may include a microporous separator material (as described above), and the microporous separator material may be oriented such that the microporous separator material is oriented along the axis A of each element 22. PE The length L of each element 22 PE In each of the exemplary embodiments described above, electrically insulating separator layer 43 also includes microporous separator material (as described above) in areas surrounding front surface 66 and back surface 68 of element 22.

[0103] In an alternative embodiment, the electrically insulating separator layer 43 is aligned along the axis A of each element 22 of the positive electrode population as described in connection with FIG. PE However, the height H of each element 21 of the negative electrode group is NE is the height H of each element 22 of the positive electrode group PE In this alternative embodiment, the electrically insulating separator layer 43 is aligned with the axis A of each element 22 of the positive electrode population. PE The length L of each element 22 of the positive electrode group PE The electrically insulating separator layer 43 also includes a microporous separator material (as described above) in areas surrounding the front surface 66 and the back surface 68 of the element 22.

[0104] 15, in one embodiment, the combination of electrically insulating separator layers 43, 86 and 88 is aligned along axis A of each element 21 of the negative electrode population. NE , and (ii) the axis A of each element 22 of the positive electrode group. PE3. Electrically insulating separator layer 43 includes a microporous separator material (as described above) in the regions between opposing outer surfaces 61, 62 and 63, 64 of each element 21, 22. Because the primary route for ion transfer between elements 21 and 22 occurs between the outer surfaces of the elements, electrically insulating separator layers 86, 88 may include any electrically insulating material suitable for use in secondary batteries, and in one such embodiment, electrically insulating separator layers 86, 88 include an electrically insulating material having low electronic and ionic conductivity for carrier ions (e.g., lithium ions). For example, in one embodiment, the electrically insulating material has a low electronic and ionic conductivity for carrier ions (e.g., lithium) of less than 1×10 -4 By way of further example, in certain embodiments the particulate material has a conductivity of 1×10 S / cm for carrier ions. -5 By way of further example, in certain embodiments the particulate material has a conductivity of less than 1×10 S / cm for carrier ions. -6 The conductive material has a conductivity of less than 1.5 S / cm. Exemplary particulate materials include any of the materials previously identified as exemplary particulate materials for the microporous separator material. In an exemplary embodiment, the combination of electrically insulating separator layers 43, 86 and 88 is aligned along axis A of each element 21. NE The length L of each element 21 NE and each element 22 has an axis A PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 70% of axis A of each element 21. NE The length L of each element 21 NE and each element 22 has an axis A PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 75% of axis A of each element 21. NE The length L of each element 21 NEand each element 22 has an axis A PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 80% of axis A of each element 21. NE The length L of each element 21 NE and each element 22 has an axis A PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 85% of axis A of each element 21. NE The length L of each element 21 NE and each element 22 has an axis A PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 90% of axis A of each element 21. NE The length L of each element 21 NE and each element 22 has an axis A PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 95% of axis A of each element 21. NE The length L of each element 21 NE The axis A of each element 22 is PE The length L of each element 22 PE Encirclement throughout.

[0105] 16, in one alternative embodiment, the combination of electrically insulating separator layers 43, 86 and 88 is aligned along axis A of each element 21 of the negative electrode population. NE15. In this embodiment, electrically insulating separator layer 43 is present between element 22 of the positive electrode population and element 21 of the negative electrode population, and electrically insulating separator layers 86, 88 are present in other regions. For example, in this embodiment, electrically insulating separator layer 43 includes a microporous separator material in the regions between opposing outer surfaces 61, 62 of each element 21, 22 and between opposing outer surfaces 63, 64 of each element 21, 22. However, because the primary route for ion transfer between element 21 and element 22 occurs between the outer surfaces of these elements, electrically insulating separator layers 86, 88 need not include a microporous separator material; instead, electrically insulating separator layers 86, 88 may optionally include an electrically insulating material that is substantially impermeable to carrier ions (e.g., lithium ions), as more fully described in connection with FIG. 15. In one such exemplary embodiment, the combination of electrically insulating separator layers 43, 86 and 88 is aligned along axis A of each element 21. NE The length L of each element 21 NE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 70% of axis A of each element 21. NE The length L of each element 21 NE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 75% of axis A of each element 21. NE The length L of each element 21 NE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 80% of axis A of each element 21. NE The length L of each element 21 NE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 85% of axis A of each element 21. NE The length L of each element 21 NE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 90% of axis A of each element 21.NE The length L of each element 21 NE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 95% of axis A of each element 21. NE The length L of each element 21 NE Encirclement throughout.

[0106] 17, in one alternative embodiment, the combination of electrically insulating separator layers 43, 86 and 88 is aligned along axis A of the positive electrode population element 22. PE 15. In this embodiment, electrically insulating separator layer 43 is present between element 22 of the positive electrode population and element 21 of the negative electrode population, and electrically insulating separator layers 86, 88 are present in other regions. For example, in this embodiment, electrically insulating separator layer 43 includes a microporous separator material in the regions between opposing outer surfaces 61, 62 of each element 21, 22 and between opposing outer surfaces 63, 64 of each element 21, 22. However, because the primary route for ion transfer between element 21 and element 22 occurs between the outer surfaces of these elements, electrically insulating separator layers 86, 88 need not include a microporous separator material; instead, electrically insulating separator layers 86, 88 may optionally include an electrically insulating material that is substantially impermeable to carrier ions (e.g., lithium ions), as will be more fully described in connection with FIG. 15. In one such exemplary embodiment, the combination of electrically insulating separator layers 43, 86 and 88 is aligned along axis A of each element 22. PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 70% of axis A of each element 22. PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 75% of axis A of each element 22. PE The length L of each element 22 PEBy way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 80% of axis A of each element 22. PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 85% of axis A of each element 22. PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 90% of axis A of each element 22. PE The length L of each element 22 PE By way of further example, the combination of electrically insulating separator layers 43, 86 and 88 in one such embodiment surrounds at least 95% of axis A of each element 22. PE The length L of each element 22 PE Encirclement throughout.

[0107] 18, in one alternative embodiment, the combination of electrically insulating separator layers 43, 86 and 88 is (i) aligned along axis A of each element 21 of the negative electrode population. NE , and (ii) the axis A of each element 22 of the positive electrode group. PE15, the electrically insulating separator layer 43 includes a microporous separator material in the area between the opposing outer surfaces 61, 62 and 63, 64 of each element 21, 22. Since the primary route for ion transfer between elements 21 and 22 occurs between the outer surfaces of these elements, the electrically insulating separator layers 86, 88 may include any electrically insulating material suitable for use in secondary batteries, and in one such embodiment, the electrically insulating separator layers 86, 88 include an electrically insulating material that is substantially impermeable to carrier ions (e.g., lithium ions), as described in connection with FIG. 15. In this embodiment, the electrically insulating separator layer 86 extends beyond the front faces 65, 66 of each element 21, 22 into the area between the opposing outer surfaces 61, 62 and 63, 64 of each element 21 and element 22. The electrically insulating separator layer 88 also extends beyond the back surfaces 67, 68 of each element 21, 22 into the areas between the opposing outer sides 61, 62 and 63, 64 of each element 21, 22. For example, in one such embodiment, the microporous separator material constitutes at least 70% by volume of the electrically insulating separator material layer 43 between the opposing outer sides 61, 62 and 63, 64 of each element 21, 22, without taking into account the porosity of the microporous separator material. By way of further example, in one embodiment, the microporous separator material constitutes at least 75% by volume of the electrically insulating separator material layer 43 between the opposing outer sides 61, 62 and 63, 64 of each element 21, 22, without taking into account the porosity of the microporous separator material. As a further example, in one embodiment, not taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 80 volume percent of the electrically insulating separator material layer 43 between the opposing outer surfaces 61, 62 and between the opposing outer surfaces 63, 64 of each element 21, 22.By way of further example, in some embodiments, without taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 85% by volume of the electrically insulating separator material layer 43 between the opposing outer surfaces 61, 62 and between the opposing outer surfaces 63, 64 of each element 21, 22. By way of further example, in some embodiments, without taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 90% by volume of the electrically insulating separator material layer 43 between the opposing outer surfaces 61, 62 and between the opposing outer surfaces 63, 64 of each element 21, 22. By way of further example, in some embodiments, without taking into account the porosity of the microporous separator material, the microporous separator material constitutes at least 95% by volume of the electrically insulating separator material layer 43 between the opposing outer surfaces 61, 62 and between the opposing outer surfaces 63, 64 of each element 21, 22.

[0108] 19, in one embodiment, electrically insulating separator layers 43, 82 and 84 surround each element 22 and each element 21 of the positive and negative electrode populations, respectively. However, in this embodiment, electrically insulating separator layer 43 is aligned with axis A of each element 22 and each element 21. PE and axis A NE are the lengths L of element 22 and element 21, respectively. PE and L NE In other words, in this embodiment, the electrically insulating separator layer 43 is present in the region between the opposing outer surfaces of each of the elements 21, 22, the electrically insulating separator layer 43 covers the front surfaces 65, 66 of each of the elements 21, 22 (see FIG. 3), and the electrically insulating separator layer 43 covers the back surfaces 67, 68 of each of the elements 21, 22 (see FIG. 3), the electrically insulating separator layer 82 is present in the region between the top portion 33 of the negative electrode 21 and the positive electrode bus bar 24, and the electrically insulating separator layer 84 is present in the region between the top portion 34 of the positive electrode 22 and the negative electrode bus bar 23. 82 corresponds to the length of the electrically insulating separator layer 82, and the length L 84 corresponds to the length of the electrically insulating separator layer 84, and the length L 43corresponds to the length of the electrically insulating separator layer 43. For example, in this embodiment, the electrically insulating separator layer 43 is (i) aligned along the axis A NE over at least a majority (e.g., at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%) of each element 21 of the negative electrode group, but over a length L NE In other words, in this embodiment, the length L 43 is the length L NE and at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% of the length L NE Furthermore, in this embodiment, the electrically insulating separator layer 43 is aligned with the axis A of each element 22 of the positive electrode population. PE over at least a majority (e.g., at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, or at least 95%) of each element 22 of the positive electrode population, but over a length L PE In other words, in this embodiment, the length L 43 is the length L PE and at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% of the length L PE 15. Electrically insulating separator layer 43 comprises a microporous separator material (as described above). However, because the primary route for ion migration between elements 21 and 22 occurs between the outer surfaces of these elements, electrically insulating separator layers 82, 84 need not comprise a microporous separator material; instead, electrically insulating separator layers 82, 84 may optionally comprise an electrically insulating material that is substantially impermeable to carrier ions (e.g., lithium ions), as more fully described in connection with FIG.

[0109] As more fully described in connection with FIG. 19, in an alternative embodiment, electrically insulating separator layer 82 is present in the region between top 33 of negative electrode 21 and positive bus bar 24, and electrically insulating separator layer 84 is present in the region between top 34 of positive electrode 22 and negative bus bar 23, but between these two regions, elements 21 and 22 may be electrically insulated along their respective lengths, as more fully described in connection with FIG. 12 et seq. In other words, in such an alternative embodiment, element 21 is surrounded by electrically insulating separator material, but element 22 is not, as more fully described in connection with FIG. 12 and FIG. 13. In another such alternative embodiment, element 22 is surrounded by electrically insulating separator material, but element 21 is not, as more fully described in connection with FIG. 14. In another such alternative embodiment, elements 21 and 22 are surrounded by electrically insulating separator layers 43, 86, and 88, as more fully described in connection with FIG. 15. In another such alternative embodiment, element 21 is surrounded by electrically insulating separator layers 43, 86, and 88, but element 22 is not, as described more fully in connection with FIG. 16. In another such alternative embodiment, element 22 is surrounded by electrically insulating separator layers 43, 86, and 88, but element 21 is not, as described more fully in connection with FIG. 17. In another such alternative embodiment, elements 21 and 22 are surrounded by electrically insulating separator layers 43, 86, and 88, as described more fully in connection with FIG. 18. In each of these embodiments, length L 43 is the length L PE and / or length L NE and at least 70%, at least 75%, at least 80%, at least 85%, at least 90% or at least 95% of the length L PE and / or length L NE Less than the total.

[0110] Referring now to FIG. 20, in an alternative embodiment, the negative electrode active material layer 49 is between the negative electrode backbone 51 and the negative electrode current collector layer 47. In this embodiment, the negative electrode current collector layer 47 comprises an ion-permeable conductor material that is both ionically conductive and electrically conductive. In other words, the negative electrode current collector layer 47 has a thickness, electrical conductivity, and ionic conductivity for carrier ions that facilitates the movement of carrier ions between the immediately adjacent negative electrode active material layer 49 on one side of the ion-permeable conductor layer in the electrochemical stack and the immediately adjacent electrically insulating separator layer 43 on the other side of the negative electrode current collector layer. In comparison, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the negative electrode current collector layer has a conductivity that is greater than its ionic conductivity. For example, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the negative electrode current collector layer is typically at least 1,000:1, respectively. By way of further example, in one such embodiment, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the negative electrode current collector layer when there is an applied current to store energy in the device or when there is an applied load to discharge the device is at least 5,000:1. By way of further example, in one such embodiment, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the negative electrode current collector layer when there is an applied current to store energy in the device or when there is an applied load to discharge the device is at least 10,000:1. By way of further example, in one such embodiment, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the negative electrode current collector layer when there is an applied current to store energy in the device or when there is an applied load to discharge the device is at least 50,000:1.By way of further example, in one such embodiment, the ratio of electrical conductivity to ionic conductivity (for carrier ions) of the negative electrode current collector layer in the presence of an applied current to store energy in the device or in the presence of an applied load to discharge the device, respectively, is at least 100,000:1.

[0111] Typically, when the negative electrode current collector layer 47 is an ionically permeable conductor layer, it has a thickness of at least about 300 angstroms. For example, in some embodiments, it may have a thickness in the range of about 300-800 angstroms. More typically, however, it has a thickness greater than about 0.1 micrometers. Typically, an ionically permeable conductor layer has a thickness of about 100 micrometers or less. Thus, for example, in some embodiments, the negative electrode current collector layer 47 has a thickness in the range of about 0.1 micrometers to about 10 micrometers. By way of further example, in some embodiments, the negative electrode current collector layer 47 has a thickness in the range of about 0.1 micrometers to about 5 micrometers. By way of further example, in some embodiments, the negative electrode current collector layer 47 has a thickness in the range of about 0.5 micrometers to about 3 micrometers. In general, it is preferred that the thickness of the negative electrode current collector layer 47 is substantially uniform. For example, in certain embodiments, the negative electrode current collector layer 47 preferably has a thickness non-uniformity of less than about 25%, where the thickness non-uniformity is defined as the amount of maximum thickness of the layer minus the minimum thickness of the layer divided by the average layer thickness. In certain embodiments, the thickness variation is even less. For example, in some embodiments, the negative electrode current collector layer 47 has a thickness non-uniformity of less than about 20%. As a further example, in some embodiments, the negative electrode current collector layer 47 has a thickness non-uniformity of less than about 15%. In some embodiments, the ionically permeable conductor layer has a thickness non-uniformity of less than about 10%.

[0112] In embodiments in which the negative electrode current collector layer 47 comprises an ionically permeable conductor material having both ionic and electrical conductivity, the negative electrode current collector layer 47 may have an ionic conductivity comparable to that of the adjacent electrically insulating separator layer 43 when there is an applied current to store energy in the device or when there is an applied load to discharge the device, such as when the secondary battery is charging or discharging. For example, in certain embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the negative electrode current collector layer 47 has an ionic conductivity (for carrier ions) that is at least 50% of that of the separator layer (i.e., a ratio of 0.5:1, respectively). As a further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the ionic conductivity (for carrier ions) of the negative electrode current collector layer 47 to that of the separator layer (for carrier ions) is at least 1:1 when there is an applied current to store energy in the device or when there is an applied load to discharge the device. By way of further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the ionic conductivity (for carrier ions) of the negative electrode current collector layer 47 to the ionic conductivity (for carrier ions) of the separator layer is at least 1.25:1. By way of further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the ionic conductivity (for carrier ions) of the negative electrode current collector layer 47 to the ionic conductivity (for carrier ions) of the separator layer is at least 1.5:1. By way of further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the ionic conductivity (for carrier ions) of the negative electrode current collector layer 47 to the ionic conductivity (for carrier ions) of the separator layer is at least 2:1.

[0113] In some embodiments, the negative electrode current collector layer 47 also has a conductivity that is substantially greater than the conductivity of the negative electrode active material layer 49. For example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the conductivity of the negative electrode current collector layer 47 to the conductivity of the negative electrode active material layer 49 is at least 100:1. By way of further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the conductivity of the negative electrode current collector layer 47 to the conductivity of the negative electrode active material layer is at least 500:1. By way of further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the conductivity of the negative electrode current collector layer 47 to the conductivity of the negative electrode active material layer is at least 1000:1. By way of further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the conductivity of the negative electrode current collector layer 47 to the conductivity of the negative electrode active material layer is at least 5000:1. By way of further example, in some embodiments, when there is an applied current to store energy in the device or when there is an applied load to discharge the device, the ratio of the conductivity of the negative electrode current collector layer 47 to the conductivity of the negative electrode active material layer is at least 10,000:1.

[0114] The thickness of the negative electrode current collector layer 47 in this embodiment (i.e., the shortest distance between the separator and the negative electrode active material layer that sandwich the ionically permeable negative electrode current collector layer 47) depends on the composition of this layer and the performance specifications of the electrochemical stack. Generally, when the negative electrode current collector layer is an ionically permeable conductor layer, it has a thickness of at least about 300 angstroms. For example, in some embodiments, it may have a thickness in the range of about 300-800 angstroms. However, more typically, it has a thickness greater than about 0.1 micrometers. Generally, ionically permeable conductor layers have a thickness of about 100 micrometers or less. Thus, for example, in some embodiments, the negative electrode current collector layer 47 has a thickness in the range of about 0.1 micrometers to about 10 micrometers. By way of further example, in some embodiments, the negative electrode current collector layer 47 has a thickness in the range of about 0.1 micrometers to about 5 micrometers. By way of further example, in some embodiments, the anode current collector layer 47 has a thickness in the range of about 0.5 micrometers to about 3 micrometers. In general, it is preferred that the thickness of the anode current collector layer 47 is substantially uniform. For example, in some embodiments, the anode current collector layer 47 preferably has a thickness non-uniformity of less than about 25%, where the thickness non-uniformity is defined as the amount of the maximum thickness of the layer minus the minimum thickness of the layer divided by the average layer thickness. In certain embodiments, the thickness variation is even less. For example, in some embodiments, the anode current collector layer 47 has a thickness non-uniformity of less than about 20%. By way of further example, in some embodiments, the anode current collector layer 47 has a thickness non-uniformity of less than about 15%. In some embodiments, the ionically permeable conductor layer has a thickness non-uniformity of less than about 10%.

[0115] In a preferred embodiment, the negative electrode current collector layer 47 is an ion-permeable conductor layer that includes conductive and ion-conductive components that contribute to ion permeability and conductivity. Typically, the conductive components include a mesh or patterned surface, a continuous conductive material in the form of a film (such as a continuous metal or metal alloy), or a composite material that includes a continuous conductive material (such as a continuous metal or metal alloy). In addition, the ion-conductive components typically include pores, such as gaps in a mesh, spaces between patterned metals or metal alloys that include metal layers, pores in a metal film or solid ion conductor that has sufficient diffusivity for carrier ions. In certain embodiments, the ion-permeable conductor layer includes a deposited porous material, an ion-transporting material, an ion-reactive material, a composite material, or a physically porous material. For example, if porous, the ion-permeable conductor layer may have a void fraction of at least about 0.25. In general, however, the void fraction typically does not exceed about 0.95. More typically, when the ionically permeable conductor layer is porous, the void fraction may be in the range of about 0.25 to about 0.85. For example, in some embodiments, when the ionically permeable conductor layer is porous, the void fraction may be in the range of about 0.35 to about 0.65.

[0116] Because it is aligned between the negative electrode active material layer 49 and the electrically insulating separator layer 43, the negative electrode current collector layer 47 may promote more uniform carrier ion transport by distributing the current from the negative electrode current collector to the surface of the negative electrode active material layer, which may promote more uniform insertion and extraction of carrier ions, and thus reduce stress in the negative electrode active material during cycling. Because the negative electrode current collector layer 47 distributes the current to the surface of the negative electrode active material layer facing the separator, the reactivity of the negative electrode active material layer to carrier ions is greatest where the carrier ion concentration is greatest.

[0117] 21, in an alternative embodiment, the positive electrode active material layer 50 is between the positive electrode backbone 52 and the positive electrode current collector layer 48. In this embodiment, the positive electrode current collector layer 48 comprises an ion-permeable conductor material that is both ionically conductive and electrically conductive. In other words, the positive electrode current collector layer has a thickness, electrical conductivity, and ionic conductivity for carrier ions that facilitates the movement of carrier ions between the immediately adjacent positive electrode active material layer 50 on one side of the ion-permeable conductor layer in the electrochemical stack and the immediately adjacent electrically insulating separator layer 43 on the other side of the positive electrode current collector layer. In comparison, in this embodiment, the positive electrode current collector layer has a conductivity greater than its ionic conductivity when there is an applied current to store energy in the device or when there is an applied load to discharge the device. For example, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the positive electrode current collector layer when there is an applied current to store energy in the device or when there is an applied load to discharge the device is typically at least 1,000:1, respectively. By way of further example, in one such embodiment, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the positive electrode current collector layer when there is an applied current to store energy in the device or when there is an applied load to discharge the device is at least 5,000:1. By way of further example, in one such embodiment, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the positive electrode current collector layer when there is an applied current to store energy in the device or when there is an applied load to discharge the device is at least 10,000:1. By way of further example, in one such embodiment, the ratio of the electrical conductivity and ionic conductivity (for carrier ions) of the positive electrode current collector layer when there is an applied current to store energy in the device or when there is an applied load to discharge the device is at least 50,000:1.By way of further example, in one such embodiment, the ratio of electrical conductivity to ionic conductivity (for carrier ions) of the positive electrode current collector layer in the presence of an applied current to store energy in the device or in the presence of an applied load to discharge the device, respectively, is at least 100,000:1.

[0118] 22, in an alternative embodiment, the negative electrode active material layer 49 is between the negative electrode backbone 51 and the negative electrode current collector layer 47, and the positive electrode active material layer 50 is between the positive electrode backbone 52 and the positive electrode current collector layer 48. In this embodiment, the negative electrode current collector layer 47 and the positive electrode current collector layer 48 comprise ion-permeable conductor materials that are both ionically conductive and electrically conductive. In other words, the negative electrode current collector layer and the positive electrode current collector layer each have a thickness, electrical conductivity, and ionic conductivity for carrier ions that facilitates the movement of carrier ions between the immediately adjacent positive electrode active material layer 50 and the negative electrode active material layer 49. In comparison, in this embodiment, the positive electrode current collector layer and the negative electrode current collector layer each have an electrical conductivity that is greater than their ionic conductivity when there is an applied current to store energy in the device or when there is an applied load to discharge the device, as described above. For example, in the presence of an applied current to store energy in the device or an applied load to discharge the device, the ratio of electrical conductivity to ionic conductivity (for carrier ions) of the positive and negative current collector layers in this embodiment will typically be at least 1,000:1, respectively.

[0119] 21 and 22, in one alternative embodiment, the negative electrode 21 comprises a negative electrode backbone 51, a negative electrode active material layer 49, a negative electrode current collector layer 47, and auxiliary negative electrode current collector layers 47A, 47B, and the positive electrode 22 comprises a positive electrode backbone 52, a positive electrode active material layer 50, a positive electrode current collector layer 48, and auxiliary positive electrode current collector layers 48A, 48B. The auxiliary negative electrode current collectors may be incorporated within the negative electrode group elements and / or positive electrode group elements to provide additional electrical conductivity.

[0120] In certain embodiments, the auxiliary negative current collector has a conductivity at least twice as high as that of the negative current collector, and in certain embodiments, the conductivity of the auxiliary negative current collector is at least five or even ten times higher than that of the negative current collector. Advantageously, the additional conductivity provided by the auxiliary negative current collector reduces the overall current collector weight and volume requirements of the negative current collector layer 47. Furthermore, when the negative current collector layer is an ionically permeable collector (as described more fully elsewhere herein), the auxiliary negative current collector conducts most of the current along the length L of the electrode. NE , and the negative current collector layer can function primarily to collect current from the electrode and provide it to the auxiliary negative current collector, thereby reducing the electronic conductivity required of the ionically permeable current collector layer and allowing the ionically permeable layer to be designed with lower electronic conductivity and higher ionic conductivity to improve cell performance.

[0121] Referring now to FIG. 23, in one embodiment, the negative electrode current collector layer 47 included in each element 21 of the negative electrode group has a length L of the element including such a negative electrode current collector. NE A length L that is at least 50% of NC As a further example, the negative electrode current collector layer 47 included in each element 21 of the negative electrode population in one embodiment has a length L of the element including such a negative electrode current collector. NE A length L that is at least 60% of NC As a further example, the negative electrode current collector layer 47 included in each element 21 of the negative electrode group in one embodiment has a length L of the element including such a negative electrode current collector. NE A length L that is at least 70% of NC As a further example, the negative electrode current collector layer 47 included in each element 21 of the negative electrode population in one embodiment has a length L of the element including such a negative electrode current collector. NE A length L that is at least 80% of NC As a further example, the negative electrode current collector layer 47 included in each element 21 of the negative electrode population in one embodiment has a length L of the element including such a negative electrode current collector. NE A length L that is at least 90% of NChas.

[0122] In some embodiments, the auxiliary negative electrode current collectors can provide a means for blocking charge / discharge reactions at predetermined locations along the electrode. The auxiliary current collectors 47A, 47B can be designed such that the ionic conductivity of this layer is near zero, thereby inhibiting charge / discharge reactions on the electrode directly below the auxiliary current collectors.

[0123] In each of the above-described embodiments, the auxiliary negative electrode current collector layers 47A and 47B each have a length L NC The length L of the negative electrode current collector layer 47 is measured in the same direction as the NC Alternatively, in each of the above-described embodiments, the auxiliary negative electrode current collector layers 47A and 47B each independently have a length equal to or substantially a portion thereof (e.g., at least 60%, at least 70%, at least 80%, or even at least 90%) of the length L NC The length L of the negative electrode current collector layer 47 is measured in the same direction as the NC The length L of each element 21 of the negative electrode group is less than a substantial part (for example, less than 40%, less than 30%, less than 20%, or even less than 10%) of the length L of each element 21 of the negative electrode group. NE will vary depending on the energy storage device and its intended use, but in many embodiments will be in the range of about 5 mm to about 500 mm. For example, in one embodiment, the length L of each element 21 NE By way of further example, the length L of each element 21 in one embodiment may range from about 10 mm to about 250 mm. NE will be in the range of about 25 mm to about 100 mm.

[0124] The auxiliary anode current collector layers 47A, 47B may comprise any of the materials previously identified in connection with the anode current collector layer 47. Because the auxiliary anode current collector layers 47A, 47B are not present between the anode active material layer and the cathode active material layer, they do not need to be ionically permeable to carrier ions. Thus, the auxiliary anode current collector layers 47A, 47B may comprise any metal or other conductor conventionally used as a current collector material for anodes, such as carbon, cobalt, chromium, copper, nickel, titanium, or alloys of one or more of these. Furthermore, in some embodiments, the auxiliary anode current collector layers 47A, 47B independently have an electrical conductivity that exceeds that of the anode current collector layer 47. For example, in some embodiments, at least one of the auxiliary anode current collector layers 47A, 47B has an electrical conductivity that is at least 200%, e.g., at least 1000%, of the electrical conductivity of the anode current collector layer.

[0125] 24, the positive electrode backbone 52, positive electrode active material layer 50, and positive electrode current collector layer 48 and auxiliary positive electrode current collector layers 48A, 48B preferably extend the majority of the distance from the bottom 32 to the top 34 of each element 22 of the negative electrode population. Auxiliary positive electrode current collectors may be incorporated within the positive electrode population elements to provide additional electrical conductivity. In certain embodiments, the auxiliary positive electrode current collector has an electrical conductivity at least twice that of the positive electrode current collector, and in certain embodiments, the electrical conductivity of the auxiliary positive electrode current collector is at least 5 or even 10 times that of the positive electrode current collector. Advantageously, the additional electrical conductivity provided by the auxiliary positive electrode current collector reduces the overall current collector weight and volume requirements of the positive electrode current collector layer 48. Furthermore, if the positive electrode current collector layer is an ionically permeable current collector (as more fully described elsewhere herein), the auxiliary positive electrode current collector will conduct most of the current along the length L of the electrode. PE and the positive current collector layer can function primarily to collect current from the electrode and provide it to the auxiliary positive current collector, thereby reducing the electronic conductivity required from the ionically permeable current collector layer and allowing for the ability to design the ionically permeable layer to have lower electronic conductivity and higher ionic conductivity for improved cell performance.

[0126] The auxiliary positive current collector layers 48A, 48B may include any of the materials identified above in connection with the positive current collector layer 48. Furthermore, in some embodiments, at least one of the auxiliary positive current collector layers 48A, 48B has an electrical conductivity that exceeds the electrical conductivity of the positive current collector layer 48. For example, in some embodiments, at least one of the auxiliary positive current collector layers 48A, 48B has an electrical conductivity that is at least 200%-1,000% of the electrical conductivity of the positive current collector layer.

[0127] In some embodiments, the auxiliary positive electrode current collectors can provide a means for blocking charge / discharge reactions at predetermined locations along the electrode. The auxiliary current collectors 48A, 48B can be designed such that the ionic conductivity of this layer is near zero, thereby inhibiting charge / discharge reactions on the electrode directly below the auxiliary current collectors.

[0128] For example, in one embodiment, the positive electrode current collector layer 48 included in each element 22 of the positive electrode population has a length L of the element including such a positive electrode current collector. PE A length L that is at least 50% of PC As a further example, the positive electrode current collector layer 48 included in each element 22 of the positive electrode population in one embodiment has a length L of the element including such a positive electrode current collector. PE A length L that is at least 60% of PC As a further example, the positive electrode current collector layer 48 included in each element 22 of the positive electrode population in one embodiment has a length L of the element including such a positive electrode current collector. PE A length L that is at least 70% of PC As a further example, the positive electrode current collector layer 48 included in each element 22 of the positive electrode population in one embodiment has a length L of the element including such a positive electrode current collector. PE A length L that is at least 80% of PC As a further example, the positive electrode current collector layer 48 included in each element 22 of the positive electrode population in one embodiment has a length L of the element including such a positive electrode current collector. PE A length L that is at least 90% of PCIn each of the above-described embodiments, the auxiliary positive electrode current collector layers 48A and 48B each have a length L PC The length L of the positive electrode current collector layer 48 is measured in the same direction as the PC Alternatively, in each of the above-described embodiments, the auxiliary positive electrode current collector layers 48A, 48B may each independently have a length equal to or substantially a portion thereof (e.g., at least 60%, at least 70%, at least 80%, or even at least 90%) of the length L PC The length L of the positive electrode current collector layer 48 is measured in the same direction as the PC The length L of each element 22 of the positive electrode group is less than a substantial part (e.g., less than 40%, less than 30%, less than 20%, or even less than 10%) of the length L of each element 22 of the positive electrode group. PE will vary depending on the energy storage device and its intended use, but in many embodiments will be in the range of about 5 mm to about 500 mm. For example, in one embodiment, the length L of each element 21 PE By way of further example, the length L of each element 21 in one embodiment may range from about 10 mm to about 250 mm. PE will be in the range of about 25 mm to about 100 mm.

[0129] The auxiliary negative current collector layers 47A, 47B and / or auxiliary positive current collector layers 48A, 48B may provide improved rate performance in certain embodiments. The auxiliary positive and / or negative current collectors may be formed on the electrode structure using methods similar to those described in connection with the formation of the positive and negative current collectors. Known methods for masking and patterning may be used in the fabrication of the backbone to selectively deposit the auxiliary current collectors at the desired locations. In some examples, deposition of the current collectors will be performed after the active electrodes are deposited to provide an ionically permeable current collection scheme.

[0130] 4 and 5, in certain embodiments, the negative electrode population elements 21 have straight sides (i.e., each side extending between the bottom 31 and the top 33 is flat). In other embodiments, the negative electrode population elements have polygonal or even curved sides (e.g., each side extending between the bottom 31 and the top 33 may be sinusoidal). In such embodiments, the length L NE is the straight line distance between the bottom 31 and the top 33.

[0131] 4 and 6, in certain embodiments, the positive electrode population elements 22 have straight sides (i.e., each side extending between the bottom 32 and the top 34 is flat). In other embodiments, the positive electrode population elements have polygonal or even curved sides (e.g., each side extending between the bottom 32 and the top 34 may be sinusoidal). In such embodiments, the length L PE is the linear distance between the bottom 32 and the top 34.

[0132] In the embodiment shown in FIG. 7, the elements 21 of the negative electrode population have a constant width W NE and a certain height H NE In another embodiment, the elements 21 of the negative electrode population have a width W that varies as a function of position along the length of the negative electrode. NE Or height H NE or the negative electrode group elements may have a cross section (along a plane perpendicular to the length direction) other than rectangular. In such other embodiments, the width W NE and height H NE refers to the maximum width and maximum height of the projection of the element 21 of the negative electrode group in a plane perpendicular to the length direction of the element 21 of the negative electrode group. In other words, the width W NE and height H NE corresponds to the length of two adjacent sides of an imaginary rectangle existing in a plane that has the smallest dimension but also includes all the points of the projections of the negative electrode group element.

[0133] In the embodiment shown in FIG. 8, the positive electrode group elements 22 have a constant width W PEand a certain height H PE In another embodiment, the elements 22 of the negative electrode population have a width W that varies as a function of position along the length of the negative electrode. PE Or height H PE or the negative electrode group elements may have a cross section (along a plane perpendicular to the length direction) other than rectangular. In such other embodiments, the width W PE and height H PE refers to the maximum width and maximum height of the projection of the element 22 of the positive electrode group in a plane perpendicular to the length direction of the element 22 of the positive electrode group. In other words, the width W PE and height H PE corresponds to the length of two adjacent sides of an imaginary rectangle existing in a plane that has a minimum dimension but includes all the points of the projections of the positive electrode group element.

[0134] 25A-25E show several alternative projections of an electrode (positive or negative) in a plane perpendicular to the length of the electrode. In Figs. 25A-25E, the projections of the electrodes describe a trapezoid (Fig. 25A), a parallelogram (Fig. 25B), a triangle (Fig. 25C), a diamond (Fig. 25D), and an ellipse (Fig. 25E). In each example, an imaginary rectangle having a minimum dimension but which still contains all the points of the electrode projections has a width W E and height H E Furthermore, in each of these examples, the electrode has a perimeter P E This means that

[0135] 26, in an alternative embodiment, an electrode stack 74 comprises three electrode structures 20 vertically stacked and aligned such that the positive electrodes 22 and the negative electrodes 21 of the three electrodes are aligned. In this embodiment, an electrically insulating material layer 86 covers the front faces 65, 66 of the elements 21, 22 of the top electrode structure in the stack, and an electrically insulating material layer 88 covers the back faces 67, 68 of the elements 21, 22 of the bottom electrode structure in the stack. As a result, each element 21 of the different electrode structures is not electrically insulated from each other, but is electrically insulated from the elements 22 of the different electrode structures in the stack. As a result, each positive electrode structure 22 is surrounded by electrically insulating material layers 43, 86 and 88, and each negative electrode structure 21 is surrounded by electrically insulating layers 43, 86 and 88. For ease of illustration, the electrode stack 74 includes only three electrode structures. As discussed in connection with FIG. 10, the electrode stack 74 may include a fewer or greater number of electrode structures 20.

[0136] 27, in an alternative embodiment, an electrode stack 74 comprises three electrode structures 20 that are vertically stacked and aligned such that an element 22 of the positive electrode population of one electrode structure is aligned with, and above and / or below, an element 21 of the negative electrode population of another electrode structure 20. In this embodiment, each element 21 and each element 22 is surrounded by an electrically insulating layer 43. For ease of illustration, the electrode stack 74 includes only three electrode structures. As described in relation to FIG. 10, the electrode stack 74 may include a fewer or greater number of electrode structures 20.

[0137] The following non-limiting examples are set forth to further illustrate the present invention. EXAMPLES

[0138] 1. Fabrication of 3D Single Cells 1. Fabrication of Comb Structure The samples used were silicon-on-insulator (SOI) wafers with layer thicknesses of 200 μm / 3 μm / 675 μm (device layer / insulation layer / backing layer). 1000 Å of Pd was sputter-deposited on top of the device layer, followed by a 2000 Å hard mask layer of silicon dioxide.

[0139] The wafer was then spin-coated with 5 μm of resist and patterned with a mask to yield an interdigitated structure having two interdigitated combs that were spaced apart from each other.

[0140] This design shows a structure that will eventually become two independent comb-shaped structures terminating in landing pads suitable for forming electrical contacts. The gap between adjacent waves was designed to be 100 microns. The length of each line was 10000 microns, and the distance between the two edges, i.e., between the end of the comb and the opposing electrical contact, was 200 microns. In other words, the distance between the top of the negative electrode comb constituting part of the negative electrode 21 and the bottom of the positive electrode comb constituting the positive electrode 22 in FIG. 9 was 200 μm. The photoresist in this pattern was then used as a photomask to remove the silicon dioxide and palladium by ion milling.

[0141] The combination of silicon dioxide, photoresist and Pd was used as a mask for silicon removal using deep reactive ion etching (DRIE) in a fluoride plasma. DRIE was performed until the silicon constituting the device layer in the mask gaps was completely removed, stopping on the oxide layer. The overetch time used to remove the silicon islands on the trench floor was 10% of the total DRIE time. The top photoresist was completely removed by stripping in acetone. At this point, the two combs are electrically isolated by DRIE.

[0142] The positive and negative pads were immersed separately in a dilute (5:1) buffered oxide etch (BOE) solution for 1 minute to remove the masking oxide layer and provide access to the palladium metal for making electrical contacts. The comb structure with the negative and positive combs separated was used as the base structure for fabricating the current collectors and electrodes.

[0143] 2. Preparation of the negative electrode current collector and negative electrode One of the isolated comb-like structure pairs (herein referred to as the negative electrode backbone comb) was electrically connected via a palladium conductor and immersed in a copper plating bath. The conditions of the copper plating bath were adjusted so that deposition (vapor deposition) occurred on the silicon layer that constituted the comb structure. The Cu layer thus deposited (vapor deposited) served as the negative electrode current collector.

[0144] The sample was immersed in an electrophoretic resist bath, and then a voltage was applied to the positive backbone comb structure. A commercial electrophoretic resist (Shipley EAGLE) was used, and the comb was electrophoretically deposited with a Pd conductor at 50 V for 120 seconds to form a resist coating. The die was baked at 120 °C for 30 minutes to harden the resist.

[0145] The silicon sample is then inserted into a deposition chamber and 20 Å of Au is deposited on the sample surface. This Au deposition process results in Au on the top of the honeycomb structure as well as on its sidewalls and the bottom oxide layer. However, due to the presence of photoresist on the positive backbone comb, the Au only comes into contact with the copper on the negative backbone comb structure. At this point, the silicon backing layer is protected with an adhesive tape mask. The sample is then immersed in acetone for 15 minutes to remove the electrophoretic resist and the Au deposited on top of the electrophoretic resist. The sample is then immersed in a dilute (5:1) buffered oxide etch (BOE) solution to remove the Au clusters and oxide layer from the insulating layer on the front of the negative comb and at the bottom of the trench. This isolates the Au nanoclusters only from the sides of the negative backbone comb.

[0146] Silicon nanowires were then grown on the sides of the anode backbone comb structure by CVD. The sample was inserted into a CVD chamber and heated to 550 °C. Silane gas was introduced into the chamber and the reactor pressure was kept at 10 Torr. The deposition rate was 4 μm per hour, and deposition was carried out to a target nanowire thickness of 20 μm. These nanowires extending out from the sides of the anode backbone comb would function as the anode of a lithium-ion battery.

[0147] 3. Preparation of Positive Current Collector and Positive Electrode The positive electrode backbone comb was then electrically connected via a palladium conductor and immersed in a gold electroplating bath to plate the palladium and silicon layers that make up the comb structure with gold. This Au layer surrounding the positive electrode backbone comb acts as the positive electrode current collector.

[0148] The cathode backbone comb was electrophoretically deposited with cathode material for lithium ion batteries. The electrophoretic deposition solution contained the cathode material (LiCoO2), 15 wt% carbon black, and 150 ppm iodine in acetone solution. The mixed solution was stirred overnight to uniformly disperse the particles. Pd contact pads were used as terminals for electrical connection of the cathode deposition. A Pt counter electrode was used. The sample was deposited at a voltage of 100 V for 3 minutes to deposit a 40 μm thick cathode structure. Deposition occurred on both the sidewalls and the front surface of the cathode comb.

[0149] 4. Removal of excess positive electrode Any excess cathode deposition on the front side of the die was removed using a mechanical removal process. The front side was lapped with an abrasive pad to expose the cathode current collector layer. This was followed by air drying to ensure that there were no stray particles on the die that could cause short circuits.

[0150] 5.1 Preparation of separator layer A porous separator is applied to the gap between the positive and negative electrodes (nominally 40 microns) using a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone and 2 volume percent PVDF binder with a final solids content of 60%. The slurry is screen printed, wetting the die to drive the particulate material between the negative and positive electrode materials. Screen printing is performed in multiple passes, with intermediate drying steps in between, to fill the trench between the negative and positive electrodes and the gaps along the top and bottom of the device (sites that constitute 82 and 84 in FIG. 19).

[0151] Any excess separator deposited on the front surface of the die was removed using a mechanical removal process. The front surface was lapped with an abrasive pad to expose the electrode current collector layer. The die was then air-dried to ensure there were no stray particles on it that could cause short circuits.

[0152] 6. Structural layer removal The top side of the die is then attached to a sacrificial glass substrate using UV release dicing tape. This setup is used to mechanically remove the backing silicon layer using conventional wafer lapping techniques. The lapping process continues until the backing wafer and intermediate oxide layer are removed. UV release is used to remove the active die from the sacrificial glass substrate, thereby preparing the die for the subsequent separator filling process.

[0153] 7.2 Preparation of separator layer An additional porous separator layer is applied to the front and back of the die by dip coating the die in a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone and 2 volume percent PVDF binder with a final solids content of 30%. The dip coated die is dried to remove the solvent and solidify the binder material (at this stage the cross section of the device looks like FIG. 15 except that there are no current collectors 47 and 48 on the bottom silicon surface). The target thickness of the front and back dip coatings was 25 microns each. EXAMPLES

[0154] 2. Fabrication of 3D Single Cells 1. Fabrication of Comb Structure The sample was a silicon wafer with a layer thickness of 200 μm. 1000 Å of Pd was sputter deposited on top of the device layer, followed by a 2000 Å hard mask layer of silicon dioxide. The wafer was flipped over and 1500 Å of Cu was deposited on the bottom side.

[0155] The sample was then anodically bonded to a borofloat glass substrate using standard anodic bonding techniques.

[0156] The wafer was then spin-coated with 5 μm of resist and patterned with a mask to yield an interdigitated structure having two spaced apart interdigitated combs as shown in FIG.

[0157] This design shows a structure that will eventually become two independent comb-shaped structures terminating in landing pads suitable for forming electrical contacts. The gap between adjacent waves was designed to be 100 microns. The length of each line was 10000 microns, and the distance between the two edges, i.e., between the end of the comb and the opposing electrical contact, was 200 microns. In other words, the distance between the top of the negative electrode comb constituting part of the negative electrode 21 and the bottom of the positive electrode comb constituting the positive electrode 22 in FIG. 9 was 200 μm. The photoresist in this pattern was then used as a photomask to remove the silicon dioxide and palladium by ion milling.

[0158] The combination of silicon dioxide, photoresist and Pd was used as a mask for silicon removal using deep reactive ion etching (DRIE) in a fluoride plasma. DRIE was performed until the silicon constituting the device layer in the mask gaps was completely removed, stopping on the oxide layer. The overetch time used to remove the silicon islands at the trench floor was 10% of the total DRIE time. The top photoresist was completely removed by stripping in acetone. The die was then immersed in a 1% nitric acid solution to remove the copper at the bottom of the trench and expose the anode glass. At this point, the two combs are electrically isolated by DRIE.

[0159] The positive and negative pads were immersed separately in a dilute (5:1) buffered oxide etch (BOE) solution for 1 minute to remove the masking oxide layer and provide access to the palladium metal for making electrical contacts. The comb structure with the negative and positive combs separated was used as the base structure for fabricating the current collectors and electrodes.

[0160] 2. Preparation of the negative electrode current collector and negative electrode The negative electrode current collector and the negative electrode were prepared by the same process as in Example 1.

[0161] 3. Preparation of Positive Current Collector and Positive Electrode The positive electrode current collector and the positive electrode were prepared by the same process as in Example 1.

[0162] 4. Preparation of Separator A porous separator is applied to the gap between the positive and negative electrodes (nominally 40 microns) using a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone and 2 volume percent PVDF binder with a final solids content of 60%. The slurry is screen printed to wet the die and drive the particulate material between the negative and positive materials. Screen printing is performed in multiple passes with intermediate drying steps in between to fill the trench between the negative and positive electrodes and the gaps along the top and bottom of the device (sites that form 82 and 84 in FIG. 19). The porous separator is then also applied to the front of the die by dip coating the die in a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone and 2 volume percent PVDF binder with a final solids content of 30%. The dip coated die is dried to remove the solvent and solidify the binder material. The target thickness of the front dip coat was 25 microns. The resulting die looks like Figure 15 except that (1) there is no current collector on the backside of 51 and 52, (2) 88 is the anode glass, and (3) 86 is a glass powder with PVDF. EXAMPLES

[0163] 3. Fabrication of 3D Single Cells 1. Fabrication of Comb Structure The comb structure was fabricated in the same manner as in Example 2.

[0164] 2. Preparation of the negative electrode current collector and negative electrode The negative electrode current collector and the negative electrode were prepared by the same process as in Example 1.

[0165] 3. Preparation of Positive Current Collector and Positive Electrode The positive electrode current collector and the positive electrode were prepared by the same process as in Example 1.

[0166] 4.1 Preparation of separator layer The separator layer was prepared by the same process as in Example 1.

[0167] 5. Structural layer removal The structural layer was removed by a process similar to that in Example 1.

[0168] 6.2 Preparation of separator layer A second separator layer was prepared by a process similar to that of Example 1, resulting in an electrode structure of the type shown in FIG. EXAMPLES

[0169] 4. Fabrication of 3D Single Cells 1. Preparation of comb structure. The comb structure was fabricated in the same manner as in Example 2, except that the anode bonding glass was a frame that contacted the negative and positive combs only at the top and bottom of the die and at the contact pads on the longitudinal axis. In other words, the longitudinal axis A in FIG. E For the majority of its length along the die, the comb lines were designed to be freestanding, in other words, most of the backside of the die was accessible for processing.

[0170] 2. Preparation of the negative electrode current collector and negative electrode The negative electrode current collector and the negative electrode were prepared by the same process as in Example 1.

[0171] 3. Preparation of Positive Current Collector and Positive Electrode The positive electrode current collector and the positive electrode were prepared by the same process as in Example 1.

[0172] 4. Removal of excess positive and negative electrode materials All excess deposited (deposited) positive and negative electrode material on the front and back sides of the die was removed using a mechanical removal process. The front side was lapped with an abrasive pad to expose the current collector layer. The back side was subjected to a doctor blade removal process to remove excess electrode material. This was followed by air drying to ensure that there were no stray particles on the die that could cause short circuits.

[0173] 5. Preparation of Separator A porous separator is applied to the gaps (nominally 40 microns) between the positive and negative electrodes, and between the front and back surfaces, using a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone and 2 volume percent PVDF binder with a final solids content of 60%. The slurry is screen printed, wetting the die and forcing the particulate material between the negative and positive materials. Screen printing is performed in multiple passes, with intermediate drying steps in between, to fill the trenches between the negative and positive electrodes, and the gaps along the top and bottom of the device (represented by 82 and 84 in Figure 19). Once this is complete, additional layers are added to provide a separator layer that also covers the front and back surfaces of the die (see Figure 3). EXAMPLES

[0174] 5. Fabrication of 3D Single Cells 1. Fabrication of Comb Structure The comb structure was fabricated in the same manner as in Example 4.

[0175] 2. Preparation of the negative electrode current collector and negative electrode The negative electrode current collector and the negative electrode were prepared by the same process as in Example 1.

[0176] 3. Preparation of Positive Current Collector and Positive Electrode The positive electrode current collector and the positive electrode were prepared by the same process as in Example 1.

[0177] 4. Removal of excess positive and negative electrode materials Excess material was removed by a process similar to that in Example 4.

[0178] 5. Preparation of Separator A commercially available, electrically insulating, two-part epoxy was dispensed with a syringe to fill the top and bottom of the die, corresponding to items 82 and 84 in Figure 19. This provides a non-porous insulating separator layer between the electrode and its counter electrode bus.

[0179] A porous separator is then applied to the gap (nominally 40 microns) between the positive and negative electrodes, front and back, using a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone and 2 volume percent PVDF binder with a final solids content of 60%. This slurry is screen printed, wetting the die and forcing the particulate material between the negative and positive electrode materials. Screen printing is performed in multiple passes, with intermediate drying steps in between, to fill the trench between the negative and positive electrodes. Once this is complete, additional layers are added to provide a separator layer that also covers the front and back of the die (see Figure 3). EXAMPLES

[0180] 6. Fabrication of 3D Single Cells 1. Fabrication of Comb Structure The comb structure was fabricated in the same manner as in Example 4.

[0181] 2. Preparation of anode current collector and cathode current collector Two current collectors were prepared in the same manner as in Example 1, except that the positive current collector was prepared immediately after the negative current collector.

[0182] 3.1 Preparation of separator layer A commercially available, electrically insulating, two-part epoxy was dispensed with a syringe to fill the top and bottom of the die, corresponding to items 82 and 84 in Figure 19. In this case, however, the epoxy coats the negative and positive current collectors, rather than the individual electrodes as in Example 5. This results in a non-porous insulating separator layer between the electrodes and their counter electrode buses.

[0183] 4. Preparation of negative electrode and positive electrode The negative and positive electrodes were prepared by the same process as in Example 4.

[0184] 5. Removal of excess positive and negative electrodes Excess material was removed by a process similar to that in Example 4.

[0185] 6.2 Preparation of separator layer A porous separator is then applied to the gaps (nominally 40 microns) between the positive and negative electrodes, and between the front and back surfaces, using a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone, and 2 volume percent PVDF binder with a final solids content of 60%. The slurry is screen printed, wetting the die and forcing the particulate material between the negative and positive materials. Screen printing is performed in multiple passes, with intermediate drying steps in between, to fill the trenches between the negative and positive electrodes, and the gaps along the top and bottom of the device (represented by 82 and 84 in FIG. 19). Once this is complete, additional layers are added to provide a separator layer that also covers the front and back surfaces of the die (see FIG. 3). EXAMPLES

[0186] 7. Fabrication of 3D Single Cells 1. Fabrication of Comb Structure A comb structure was fabricated similar to Example 4, except that the gap between the negative and positive combs was reduced to 80 microns instead of 100 microns, and the negative comb layer was widened by 40 microns.

[0187] 2. Preparation of the negative electrode and negative electrode current collector One of the isolated comb structures (herein referred to as the positive backbone comb) was immersed in an electrophoretic resist bath. A commercial electrophoretic resist (Shipley EAGLE) was used to electrophoretically deposit the positive backbone comb with Pd conductor at 50V for 120 seconds to form a resist coating. The die was baked at 120°C for 30 minutes to harden the resist.

[0188] The silicon sample is then inserted into a deposition chamber to deposit 100 Å of Au on the sample surface. This Au deposition process results in Au on the top of the combs, their sidewalls, and the bottom oxide layer. However, due to the presence of photoresist on one of the combs, the Au only comes into contact with the silicon on one of the two comb structures. At this point, the silicon backing layer is protected with an adhesive tape mask. The sample is then immersed in a 1:1 by volume solution of hydrofluoric acid (49%) and hydrogen peroxide (30%) at 30°C to form a porous silicon layer. The etching time was varied to control the depth of the porous silicon. The rate of porous silicon formation was about 750-1000 nm per minute. The parts were removed and dried when the target pore depth of 20 μm was reached.

[0189] Porous silicon is formed only on the comb set where the electrophoretic resist was not patterned. This porous silicon set is used as the negative electrode in a lithium-ion battery. The electrophoretic resist was then stripped in acetone for 15 minutes.

[0190] The negative backbone comb was then electrically connected via a palladium conductor and immersed in a copper plating bath consisting of very dilute (10 mM) copper sulfate and sulfuric acid. The conditions in the copper plating bath were adjusted so that deposition occurred both on the palladium and on the porous silicon. The copper concentration was kept low so that copper deposition was transport limited along the outer layer of the porous silicon, which was porous. This Cu layer served as the negative current collector, which was also ion-permeable due to its porosity. However, the copper on the Pd layer was thicker and non-porous to act as a secondary bussing collector for the negative electrode.

[0191] 3. Preparation of Positive Current Collector and Positive Electrode The positive electrode current collector and the positive electrode were prepared by the same process as in Example 1.

[0192] 4. Removal of excess positive and negative electrodes Excess material was removed by a process similar to that in Example 4.

[0193] 5. Preparation of Separator A porous separator is then applied to the gaps (nominally 40 microns) between the positive and negative electrodes, and between the front and back surfaces, using a slurry containing fine glass powder (less than 2 microns in diameter) dispersed in N-methylpyrrolidone and 2 volume percent PVDF binder with a final solids content of 60%. The slurry is screen printed, wetting the die and forcing the particulate material between the negative and positive materials. Screen printing is performed in multiple passes, with intermediate drying steps in between, to fill the trenches between the negative and positive electrodes, and the gaps along the top and bottom of the device (represented by 82 and 84 in FIG. 19). Once this is complete, additional layers are added to provide a separator layer that also covers the front and back surfaces of the die (see FIG. 20). EXAMPLES

[0194] 8. Fabrication of 3D Single Cells 1. Fabrication of Comb Structure The comb structure was fabricated in the same manner as in Example 4.

[0195] 2. Preparation of the negative electrode and negative electrode current collector A negative electrode current collector was produced using the same process as in Example 1.

[0196] A negative backbone comb was used to electrophoretically deposit graphite particles onto the comb surface using a non-aqueous electrophoretic deposition slurry. The deposition slurry consisted of graphite particles (mesocarbon microbeads, 95 wt%) and carbon black (5 wt%) dispersed in acetone with 25 ppm iodine as a charging agent. Electrophoretic deposition was performed at 100 V for 180 seconds using a platinum counter electrode, depositing an average film thickness of 60 microns.

[0197] Before proceeding to the next step, all excess negative electrode on the front and back sides of the negative comb was removed by mechanical grinding.

[0198] 3. Preparation of Separator An electrophoretic deposition slurry for aluminum oxide particles was prepared as shown below. 3 wt% aluminum oxide microparticles were added to 97 wt% ethanol and stirred for 2 hours. 0.05 wt% polyvinyl butyral (calculated from the total amount of aluminum oxide and ethanol) was added to the above slurry. The pH of the solution was adjusted to 1.5 using hydrochloric acid. The resulting mixture was stirred overnight.

[0199] The comb assembly was then immersed in the electrophoretic deposition bath and an electric field was applied between the negative and positive combs. The Au-plated positive current collector comb served as the counter electrode for the electrophoretic deposition process. The working electrode for the separator deposition was the negative comb with the negative electrode on top. The deposition current was kept constant at 2 mA / cm2 at the current collector site and the current was turned on for 1800 seconds. This resulted in a 40 micron thick layer of aluminum oxide and polyvinyl butyral around the electrophoretically deposited negative electrode.

[0200] 4. Preparation of Positive Electrode Current Collector A positive electrode current collector was produced by the same process as in Example 1.

[0201] 5. Preparation of Positive Electrode The die was then coated with a slurry of lithium ion cathode material of the following composition: 80 g lithium cobalt oxide, 5 g graphite, 5 g carbon black, and 10 g PVDF, all mixed in a 1:2 volume ratio of N-methylpyrrolidone and acetone as fast drying solvents. The slurry was dried and the solvent evaporated, leaving the conductive cathode material. This material was then lapped onto the comb surface, exposing the separator material on the front and back of the sample. EXAMPLES

[0202] Creating a 3D battery 1 1. Single Die Preparation The contact pads used to fabricate the die in Examples 1-8 were removed by dicing with a dicing saw, leaving the negative and positive bus connections intact. All of the separator material covering the edges of the die and overlying the bus lines was removed to expose the current collector material, which was Cu for the negative electrode and Au for the positive electrode.

[0203] 2. Connecting the tab extension Following exposure of the current collectors, the tab extensions were attached onto the negative and positive busses. The gold bus lines were attached to the aluminum tabs using a commercial carbon adhesive (DAG-T-502). The tab extensions were coated with a thin carbon layer and glued to the sides of the gold busses. The nickel tab extensions were glued to the copper current collector busses using the same commercial carbon adhesive. The adhesive was baked at 120°C for 1 hour to cure. The tab extensions also included the tabs that would emerge from the package. The tab extensions were folded and flattened horizontally in preparation for packaging.

[0204] 3. Battery packaging and electrolyte filling The die with two tab extensions was inserted into a commercially available battery pouch packaging material. The pouch material was sealed on the tab side, including the tab. One of the other three sides was left open to provide a port for electrolyte filling. A vacuum was applied and a conventional electrolyte containing propylene carbonate, ethylene carbonate, and ethyl methyl carbonate in a 1:1:3 ratio, and lithium hexafluorophosphate salt (1M) was added to the cell in the glove box. The last side of the pouch was then sealed while the die was inside the glove box to prevent moisture and oxygen from entering the pouch and causing loss of battery life. The battery was then charged and discharged using a commercially available battery cycler. EXAMPLES

[0205] 1. Fabrication of 3D Stacked Battery 1. Single die preparation: The single die preparation process was carried out similarly to Example 5, but for three different dies separately. The contact pads on the dies were removed similarly to Example 9. The dies were then stacked one on top of the other such that the electrodes were aligned.

[0206] 2. Tab extension connection: Following exposure of the current collectors, the tab extensions were attached onto the negative and positive busses. The gold bus lines were attached to the aluminum tabs using a commercial carbon adhesive (DAG-T-502). The tab extensions were coated with a thin carbon layer and glued to the sides of the gold busses. The nickel tab extensions were glued to the copper current collector busses using the same commercial carbon adhesive. The adhesive was baked at 120°C for 1 hour to cure. The tab extensions also included the tabs that would emerge from the package. The tab extensions were folded and flattened horizontally in preparation for packaging.

[0207] 3. Battery packaging and electrolyte filling: Packaging of the battery and filling of the electrolyte were carried out as in Example 9. EXAMPLES

[0208] 1. Fabrication of 3D Parallel Cells 1. Single die preparation: The preparation process of a single die was carried out similarly to that in Example 5, but for two different dies separately.

[0209] 2. Tab extension connection: The tab extensions were connected using the same conductive adhesive as in Example 9, except that the die were aligned such that adjacent positive bus connections were connected with a single tab extension between them.

[0210] 3. Battery packaging and electrolyte filling: Packaging of the battery and filling of the electrolyte were carried out as in Example 9.

[0211] In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained.

[0212] When expanding upon elements of the present invention or preferred embodiments of the present invention, the indefinite article, definite article and "said" are intended to mean the presence of one or more elements. The words "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements other than the listed elements.

[0213] Various changes may be made in the above-described items, compositions and methods without departing from the scope of the present invention, and it is therefore intended that all matters set forth in the above specification and shown in the accompanying drawings be interpreted as illustrative and not limiting.

Claims

1. An electrode structure comprising an electrode group having an electrode active material layer and a counter electrode group having a counter electrode active material layer, The electrodes are arranged alternately with the counter electrodes along a first direction; Each element of the electrode group has a bottom, a top, and a length L Ｅ and width W Ｅ and height H Ｅ and a longitudinal axis A extending from the bottom to the top of the element in a direction intersecting the first direction. Ｅ and the length L of each element of the electrode group. Ｅ is its longitudinal axis A Ｅ The width W of each element of the electrode group is measured in the direction Ｅ is measured in the first direction, and the height H Ｅ is the longitudinal axis A of the element Ｅ and L of each element of the electrode group measured in a direction perpendicular to the first direction. Ｅ And W Ｅ and H Ｅ and the ratio of H to H of each element of the electrode group is at least 5:1, Ｅ And W Ｅ and the ratio of is between 0.4:1 and 1000:1, respectively; The longitudinal axis A of each element of the electrode group Ｅ is surrounded by an electrically insulating separator layer; and An electrode structure, wherein between an element of the electrode population and an element of the counter-electrode population, the electrically insulating separator layer comprises a microporous separator material having a void fraction of at least 20% by volume.

2. 2. The electrode structure of claim 1, wherein between an element of the electrode population and an element of the counter-electrode population, the microporous separator material comprises at least 70% by volume of the electrically insulating separator material layer.

3. 2. The electrode structure of claim 1, wherein between an element of the electrode population and an element of the counter-electrode population, the microporous separator material constitutes at least 80% by volume of the electrically insulating separator material layer.

4. 2. The electrode structure of claim 1, wherein between an element of the electrode population and an element of the counter-electrode population, the microporous separator material constitutes at least 90% by volume of the electrically insulating separator material layer.

5. 2. The electrode structure of claim 1, wherein between an element of the electrode population and an element of the counter-electrode population, the microporous separator material constitutes at least 95% by volume of the electrically insulating separator material layer.

6. The microporous separator material is aligned along the longitudinal axis A of each element of the electrode group. Ｅ The electrode structure according to any one of claims 1 to 5, which surrounds

7. The microporous separator material is aligned along the longitudinal axis A of each element of the electrode group. Ｅ the length L of each element of the electrode group Ｅ 6. The electrode structure according to claim 1, wherein the electrode surrounds at least 70% of the surface of the substrate.

8. The microporous separator material is aligned along the longitudinal axis A of each element of the electrode group. Ｅ the length L of each element of the electrode group Ｅ 6. The electrode structure according to claim 1, wherein the electrode surrounds at least 80% of the surface of the substrate.

9. The microporous separator material is aligned along the longitudinal axis A of each element of the electrode group. Ｅ the length L of each element of the electrode group Ｅ 6. The electrode structure according to claim 1, wherein the electrode surrounds at least 90% of the surface of the substrate.

10. The microporous separator material is aligned along the longitudinal axis A of each element of the electrode group. Ｅ the length L of each element of the electrode group Ｅ 6. The electrode structure according to claim 1, wherein the electrode surrounds at least 95% of the surface of the substrate.

11. The microporous separator material is aligned along the longitudinal axis A of each element of the electrode group. Ｅ the length L of each element of the electrode group Ｅ 6. The electrode structure according to claim 1, which is entirely surrounding.

12. The microporous separator material is aligned along the longitudinal axis A of each element of the electrode group. Ｅ and the upper portion of each element of the electrode group.

13. 13. The electrode structure of claim 1, wherein the electrically insulating material layer comprises the microporous separator material and a second electrically insulating material.

14. 6. The electrode structure of claim 1, wherein the top of each element of the electrode group is coated with the electrically insulating separator layer, and the electrically insulating separator layer comprises a microporous separator material that constitutes at least 70 volume % of the electrically insulating separator material layer between the element of the electrode group and the element of the counter-electrode group.

15. 15. The electrode structure of claim 1, wherein the electrode group has N elements and the counter-electrode group has N+1 elements, and N is at least 5.

16. 16. The electrode structure of claim 1, wherein the counter electrode group has N elements and the electrode group has N+1 elements, and N is at least 5.

17. 17. The electrode structure of claim 1, wherein the population of electrodes and the population of counter-electrodes each include at least 50 elements.

18. L Ｅ 18. The electrode structure of claim 1, wherein has a value within the range of about 10 mm to about 250 mm.

19. W Ｅ 19. The electrode structure of claim 1, wherein has a value in the range of about 0.01 mm to about 2.5 mm.

20. H Ｅ 20. The electrode structure of claim 1, wherein has a value in the range of about 0.05 mm to about 10 mm.

21. In each element of the electrode group, L Ｅ And W Ｅ and H Ｅ 21. The electrode structure of claim 1, wherein the ratio of each of said at least one of said first and second electrodes to each of said at least one of said first and second electrodes is at least 10:

1.

22. The cross section of each element of the electrode group has a circumference P Ｅ and in each element of the electrode group, L Ｅ and P Ｅ 22. The electrode structure of claim 1, wherein the ratio of 0.1 to 0.25 is at least 1.25:

1.

23. Each element of the counter electrode group has a bottom, a top, and a length L ＣＥ and width W ＣＥ and height H ＣＥ and a longitudinal axis A extending from the bottom to the top of the element in a direction intersecting the first direction. ＣＥ and the length L of each element of the electrode group. ＣＥ is its longitudinal axis A ＣＥ The width W of each element of the electrode group is measured in the direction ＣＥ is measured in the first direction, and the height H ＣＥ is the longitudinal axis A of the element ＣＥ and L of each element of the electrode group measured in a direction perpendicular to the first direction. ＣＥ And W ＣＥ and H ＣＥ and the ratio of H of each element of the electrode group is at least 5:1, ＣＥ And W ＣＥ 23. The electrode structure of claim 1, wherein the ratio of 0.4:1 to 1000:1, respectively.

24. L ＣＥ 24. The electrode structure of claim 1, wherein has a value within the range of about 10 mm to about 250 mm.

25. W ＣＥ 25. The electrode structure of claim 1, wherein has a value within the range of about 0.01 mm to 2.5 mm.

26. H ＣＥ 26. The electrode structure of claim 1, wherein has a value in the range of about 0.05 mm to about 10 mm.

27. In each element of the electrode group, L ＣＥ And W ＣＥ and H ＣＥ 27. The electrode structure of claim 1, wherein the ratio of each of said at least one of said first and second electrodes to each of said at least one of said first and second electrodes is at least 10:

1.

28. The cross section of each element of the counter electrode group has a circumference P ＣＥ and in each element of the counter electrode group, L ＣＥ and P ＣＥ 28. The electrode structure of claim 1, wherein the ratio of N to N is at least 1.25:1, respectively.

29. 29. The electrode structure of claim 1, wherein each element of the electrode group further comprises an electrode backbone.

30. 30. The electrode structure of claim 1, wherein each element of the electrode group further comprises an electrode trunk, the electrode trunk of each element of the electrode group having a conductivity of less than 10 Siemens / cm.

31. 31. The electrode structure of claim 29 or 30, wherein in each element of the electrode group, the electrode current collector layer is between the electrode active material and the electrode backbone, and the electrode active material is between the microporous separator and the electrode current collector layer.

32. 31. The electrode structure of claim 29 or 30, wherein in each element of the electrode group, the electrode current collector layer comprises an ion-permeable conductive material and is located between the electrode active material and the microporous separator, and the electrode active material is between the electrode current collector layer and the electrode backbone.

33. 33. The electrode structure of claim 32, wherein in each member of the electrode population, the electrode current collector layer has electrical conductivity and ionic conductivity to carrier ions, and the ratio of the electrical conductivity of the electrode current collector layer to the ionic conductivity to carrier ions of the electrode current collector layer is at least 1,000:1, respectively, in the presence of an applied current to store energy in the electrode structure or in the presence of an applied load to discharge the electrode structure.

34. 34. The electrode structure of claim 1, wherein in each element of the electrode group, the electrode current collector layer and the electrode active material layer are electrically conductive, and the ratio of the electrical conductivity of the electrode current collector layer to the electrical conductivity of the electrode active material layer is at least 100:1, respectively.

35. Each element of the electrode group has a length L of the electrode current collector layer included in the element. Ｅ－Ｃ 35. The electrode structure of claim 1, further comprising a complementary electrode current collector layer having a length that is at least 60% of the length of the electrode current collector layer and a conductivity that is at least 200% of the conductivity of the electrode current collector layer contained in the element.

36. 36. The electrode structure of claim 1, wherein each member of the population of counter electrodes further comprises an electrode backbone.

37. 37. The electrode structure of claim 36, wherein the backbone of each member of the population of counter electrodes has a conductivity of less than 10 Siemens / cm.

38. 38. The electrode structure of claim 36 or 37, wherein in each member of the counter electrode population, the counter electrode current collector layer is between the counter electrode active material and the counter electrode backbone, and the electrode active material is between the microporous separator and the counter electrode current collector layer.

39. 38. The electrode structure of claim 36 or 37, wherein in each member of the counter electrode population, the counter electrode current collector layer comprises an ion-permeable conductive material and is located between the counter electrode active material and the microporous separator, and the counter electrode active material is between the counter electrode current collector layer and the counter electrode backbone.

40. 40. The electrode structure of claim 39, wherein in each member of the population of counter electrodes, the counter electrode current collector layer is electrically conductive and ionic conductive to carrier ions, and the ratio of the electrical conductivity of the counter electrode current collector layer to the ionic conductivity of the counter electrode current collector layer to carrier ions is at least 1,000:1, respectively, when there is an applied current to store energy in the electrode structure or when there is an applied load to discharge the electrode structure.

41. 41. The electrode structure of claim 1, wherein in each element of the counter electrode group, the counter electrode current collector layer and the counter electrode active material layer are electrically conductive, and the ratio of the electrical conductivity of the counter electrode current collector layer to the electrical conductivity of the counter electrode active material layer is at least 100:1, respectively.

42. Each element of the counter electrode group has a length L of the counter electrode current collector layer included in the element. Ｅ－Ｃ 42. The electrode structure of claim 1, further comprising an auxiliary counter electrode current collector layer having a length that is at least 60% of the length of the counter electrode current collector layer and a conductivity that is at least 200% of the conductivity of the counter electrode current collector layer contained in the element.

43. 43. The electrode structure of claim 1, further comprising an electrode substrate having a surface to which each member of the electrode group is directly attached.

44. The electrode structure described in any one of claims 1 to 43, further comprising an electrode substrate having a surface to which each element of the electrode group is directly attached, and a counter electrode substrate having a surface to which each element of the counter electrode group is attached, the surface of the electrode substrate and the surface of the counter electrode substrate being opposing surfaces approximately parallel to the first direction.

45. 45. The electrode structure of claim 1, wherein the population of electrodes is a population of negative electrodes, the population of counter electrodes is a population of positive electrodes, the electrode active material layer is a negative electrode active material layer, and the electrode current conductor layer is a negative electrode current conductor layer.

46. 46. ​​The electrode structure of claim 45, wherein the negative electrode active material layer comprises carbon, aluminum, tin, silicon, or alloys thereof.

47. 46. ​​The electrode structure of claim 45, wherein the negative electrode active material layer comprises silicon or an alloy thereof.

48. 46. ​​The electrode structure of claim 45, wherein the negative electrode active material layer comprises nanowires of silicon or its alloys, or porous silicon or its alloys.

49. 45. The electrode structure of claim 1, wherein the group of electrodes is a group of positive electrodes.

50. The electrode group is a group of negative electrodes, and the counter electrode group is a group of positive electrodes, each element of the negative electrode group includes a negative electrode active material layer and a negative electrode current conductor layer, and each element of the negative electrode group has a bottom, a top, and a length L ＮＥ and width W ＮＥ and height H ＮＥ and the length L ＮＥ is measured from the bottom to the top of each negative electrode, and the width W ＮＥ and the height H ＮＥ are perpendicular to each other, and the length L ＮＥ Measured in a direction perpendicular to the measurement direction of L ＮＥ And W ＮＥ and H ＮＥ is at least 5:1 with each of H ＮＥ And W ＮＥ and the negative electrode current collector layer of each member of the group has a ratio of L ＮＥ Measured in the same direction as L ＮＥ A length L that is at least 50% of ＮＣ The electrode structure of claim 1 , comprising:

51. The electrode group is a group of positive electrodes, and the counter electrode group is a group of negative electrodes, each element of the positive electrode group includes a positive electrode active material layer and a positive electrode current conductor layer, and each element of the positive electrode group has a bottom, a top, and a length L ＰＥ and width W ＰＥ and height H ＰＥ and the length L ＰＥ is measured from the bottom to the top of each positive electrode, and the width W ＰＥ and the height H ＰＥ are perpendicular to each other, and the length L ＰＥ Measured in a direction perpendicular to the measurement direction of L ＰＥ And W ＰＥ and H ＰＥ is at least 5:1 with each of H ＰＥ And W ＰＥ The ratio of the positive electrode current collector layer to the positive electrode current collector layer of each member of the positive electrode population is between 0.4:1 and 1000:

1. ＰＥ Measured in the same direction as L ＰＥ A length L that is at least 50% of ＰＣ The electrode structure of claim 1 , comprising:

52. 52. The electrode structure of claim 1, wherein the microporous separator material layer comprises a particulate material and a binder.

53. An electrode stack comprising at least two electrode structures according to any one of claims 1 to 52.

54. 54. The electrode stack of claim 53, wherein the electrode structures are stacked vertically, such that the positive and negative electrode populations included in a first electrode structure in the electrode stack reside in a different plane than the positive and negative electrode populations included in a second electrode structure in the electrode stack.

55. 54. The electrode stack of claim 53, wherein the electrode structures are arranged horizontally, such that the positive electrode group and the negative electrode group included in a first electrode structure in the electrode stack are in approximately the same plane as the positive electrode group and the negative electrode group included in a second electrode structure in the electrode stack.

56. A secondary battery comprising: a battery case; a non-aqueous electrolyte; and the electrode structure according to any one of claims 1 to 52 or the electrode laminate according to any one of claims 53 to 55.

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