Current collector with surface structure for controlling the formation of solid electrolyte interface layer

Abstract

This application relates to a current collector having a surface structure for controlling the formation of a solid electrolyte interface layer. This disclosure provides an electrochemical battery comprising a conductive material layer, a precursor material disposed on or adjacent to a first surface of the conductive material layer, and an electroactive material layer disposed on or adjacent to the precursor material. In some variations, the precursor material forms a continuous layer and the solid electrolyte interface layer is disposed on or adjacent to an exposed surface of the electroactive material layer. In other variations, the precursor material forms a plurality of different precursor structures arranged in a predetermined pattern on the first surface of the conductive material layer, such that at least a portion of each different precursor structure is not obstructed by the electroactive material layer. The different precursor structures are configured to form a surface structure chemically connecting the solid electrolyte interface layer and the conductive material layer.

Description

Technical Field

[0001] This disclosure relates to current collectors having surface structures that facilitate control over the formation of solid-state electrolyte layers in electrochemical cells including said current collectors. This disclosure also relates to electrochemical cells including said current collectors. Background Technology

[0002] This section provides background information relating to this disclosure, which is not necessarily prior art.

[0003] Advanced energy storage devices and systems are needed to meet the energy and / or power requirements of various products, including automotive products such as start-stop systems (e.g., 12V start-stop systems), battery auxiliary systems, hybrid electric vehicles ("HEVs"), and electric vehicles ("EVs"). A typical lithium-ion battery pack includes at least two electrodes and an electrolyte and / or separator. One of the two electrodes may act as a positive electrode or cathode, and the other electrode may act as a negative electrode or anode. The separator and / or electrolyte may be disposed between the negative and positive electrodes. The electrolyte is adapted to conduct lithium ions (or sodium ions in the case of a sodium-ion battery pack, or potassium ions in the case of a potassium-ion battery pack, or magnesium ions in the case of a magnesium-ion battery pack, etc.) between the electrodes and, like the two electrodes, may be in solid and / or liquid form and / or mixtures thereof. In the case of solid-state battery packs (which include solid electrodes and solid electrolytes), the solid electrolyte can physically separate the electrodes, thus eliminating the need for separate separators.

[0004] Conventional rechargeable lithium-ion battery packs operate by reversibly transferring lithium ions back and forth between the negative and positive electrodes. For example, during charging, lithium ions can move from the positive to the negative electrode and in the opposite direction when the battery pack discharges. Such lithium-ion battery packs can reversibly supply power to the relevant load device on demand. More specifically, the lithium-ion battery pack can supply electrical energy to the load device until the lithium content at the negative electrode is effectively depleted. The battery pack can then be recharged by transferring a suitable direct current in the opposite direction between the electrodes.

[0005] During discharge, the negative electrode may contain a relatively high concentration of intercalated lithium or lithium metal, which is typically oxidized to lithium ions, releasing electrons. These lithium ions can be transported from the negative electrode to the positive electrode, for example, through an ion-conducting electrolyte solution contained within the pores of an inserted porous separator. Simultaneously, electrons are transferred from the negative electrode to the positive electrode via an external circuit. Such lithium ions can typically be assimilated into the positive electrode material through an electrochemical reduction reaction. After partially or fully discharging at its usable capacity, the battery pack can be recharged or regenerated by an external power source, reversing the electrochemical reactions that occurred during discharge.

[0006] However, in various cases, a portion of lithium remains with the negative electrode after the first cycle due to conversion reactions, for example, during the first cycle, and / or the formation of a solid electrolyte interphase (SEI) layer on the negative electrode, as well as continuous lithium loss due to, for example, the breakdown of the continuous SEI layer. This permanent loss of lithium ions can lead to reduced specific energy and power in the battery pack, as the positive electrode mass increases, for example, and does not participate in the reversible operation of the battery pack. For example, lithium-ion battery packs can experience irreversible capacity loss of greater than or equal to about 5% to less than or equal to about 30% after the first cycle, and in the case of silicon-containing negative electrodes, the irreversible capacity loss after the first cycle is greater than or equal to about 20% to less than or equal to about 40%. Therefore, it is desirable to develop improved electrodes and electroactive materials that can address these challenges, as well as methods for preparing and using them. Summary of the Invention

[0007] This section provides a general overview of this disclosure, rather than a full disclosure of its entire scope or all its features.

[0008] This disclosure relates to current collectors having surface structures that facilitate control over the formation of a solid electrolyte layer in an electrochemical cell including the current collector.

[0009] In various aspects, this disclosure provides a current collector for an electrochemical cell. The current collector includes a conductive material layer and a precursor material disposed on or adjacent to a first surface of the conductive material layer, wherein the precursor material has a density of less than about 10. -4 Ionic conductivity in S / cm.

[0010] In one aspect, the precursor material may be disposed on or adjacent to a first surface of the conductive material to form a substantially continuous layer. The substantially continuous layer may have an average thickness greater than or equal to about 0.001 µm and less than or equal to about 20 µm.

[0011] In one aspect, the precursor material may be disposed on or adjacent to the first surface of the conductive material to form a plurality of different precursor structures on the first surface of the conductive material layer. The different precursor structures may be disposed on the first surface of the conductive material layer in a predetermined pattern.

[0012] In one aspect, the different precursor structures may cover a total surface area of ​​the first surface of the conductive material layer that is greater than or equal to about 1% to less than or equal to about 50%.

[0013] In one aspect, the different precursor structures may have an average spacing of more than or equal to about 0.1 µm to less than or equal to about 50 µm.

[0014] In one aspect, the precursor material includes one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), perfluoro-organosiloxane, and combinations thereof.

[0015] In various aspects, this disclosure provides an electrochemical battery. The electrochemical battery may include a conductive material layer, a precursor material disposed on or adjacent to a first surface of the conductive material layer, and an electroactive material layer disposed on or adjacent to the precursor material. The non-conductive material may have a density of less than about 10. -4 Ionic conductivity in S / cm.

[0016] In one aspect, the precursor material may be disposed on or adjacent to a first surface of the conductive material to form a substantially continuous layer. The substantially continuous layer may have an average thickness greater than or equal to about 0.001 µm and less than or equal to about 20 µm.

[0017] In one aspect, the electrochemical cell may further include a solid-electrolyte interface layer disposed on or adjacent to the exposed surface of the electroactive material layer.

[0018] In one aspect, the solid electrolyte interface layer may include one or more materials selected from the group consisting of lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefins, semicarbonates, and combinations thereof.

[0019] In one aspect, the precursor material may be disposed on or adjacent to the first surface of the conductive material layer to form a plurality of different precursor structures disposed in a predetermined pattern on the first surface of the conductive material layer.

[0020] In one aspect, at least a portion of each different precursor structure may be unobstructed by the electroactive material layer.

[0021] In one aspect, at least a portion of each different precursor structure may extend through the electroactive material layer.

[0022] In one aspect, the different precursor structures may cover a total surface area of ​​the first surface of the conductive material layer that is greater than or equal to about 1% to less than or equal to about 50%.

[0023] In one aspect, the different precursor structures may have an average spacing of more than or equal to about 0.1 µm to less than or equal to about 50 µm.

[0024] In one aspect, the average height of each different precursor structure is greater than or equal to about 20% to less than or equal to about 400% higher than the average thickness of the electroactive material layer.

[0025] In one aspect, the average height of each different precursor structure may be greater than about 1 µm to less than or equal to about 500 µm, and the electroactive material layer may have an initial thickness greater than about 10 µm to less than or equal to about 200 µm.

[0026] In one aspect, the electrochemical cell may further include a solid electrolyte interface layer disposed on or adjacent to the exposed surface of the electroactive material layer and in contact with each of the different precursor structures. The different precursor structures may be configured to form surface structures that chemically bond the solid electrolyte interface layer and the conductive material layer.

[0027] In one aspect, the solid electrolyte interface layer may include one or more materials selected from the group consisting of lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefins, hemicarbonates, and combinations thereof.

[0028] In one aspect, the precursor material may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), perfluoroorganosiloxanes, and combinations thereof.

[0029] In various aspects, this disclosure provides an electrochemical cell. The electrochemical cell may include a conductive material layer, a plurality of different precursor structures disposed in a predetermined pattern on a first surface of the conductive material layer, and an electroactive material layer disposed on or adjacent to the precursor materials such that at least a portion of each different precursor structure is not obstructed by the electroactive material layer. The different precursor structures may cover a total surface area of ​​the first surface of the conductive material layer that is greater than or equal to about 1% and less than or equal to about 50%, and the different precursor structures may have an average spacing of greater than or equal to about 0.1 µm and less than or equal to about 50 µm.

[0030] In one aspect, at least a portion of each different precursor structure may extend through the electroactive material layer.

[0031] In one aspect, the electrochemical cell may further include a solid electrolyte interface layer disposed on or adjacent to the exposed surface of the electroactive material layer and in contact with each of the different precursor structures. The different precursor structures may be configured to form surface structures that chemically bond the solid electrolyte interface layer and the conductive material layer.

[0032] In one aspect, the solid electrolyte interface layer may include one or more materials selected from the group consisting of lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefins, hemicarbonates, and combinations thereof.

[0033] In one aspect, each of the different precursor structures may include one or more materials selected from: polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), perfluoroorganosiloxanes, and combinations thereof.

[0034] In various aspects, this disclosure provides an electrochemical battery. The electrochemical battery may include a conductive material layer, an electroactive material layer disposed on or adjacent to an exposed surface of the conductive material layer, a solid electrolyte interface layer disposed on or adjacent to an exposed surface of the electroactive material layer, and a plurality of different surface structures that are freely accessible through the electroactive material layer and chemically bonded to a first surface of the conductive material layer and the solid electrolyte interface layer.

[0035] In one aspect, the plurality of surface structures may comprise lithium fluoride (LiF).

[0036] In one aspect, the solid electrolyte interface layer may include one or more materials selected from the group consisting of lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefins, hemicarbonates, and combinations thereof.

[0037] In one aspect, the different surface structures may cover a total surface area of ​​the first surface of the conductive material layer that is greater than or equal to about 1% to less than or equal to about 50%.

[0038] In one aspect, the different surface structures may have an average spacing of more than or equal to about 0.1 µm to less than or equal to about 50 µm.

[0039] In various aspects, this disclosure provides a method for securing a solid electrolyte interface layer. The method may include disposing a precursor material on or adjacent to a conductive material layer. The precursor material may have a density of less than about 10. -4 The method may further include disposing an electroactive material layer on or adjacent to the precursor material. The precursor material may be configured to form a surface structure that chemically bonds the conductive material layer and the solid electrolyte interface layer, the solid electrolyte interface layer being disposed on or formed on the exposed surface of the electroactive material layer.

[0040] In one aspect, the precursor material may be disposed on or adjacent to a first surface of the conductive material to form a substantially continuous layer. The substantially continuous layer may have an average thickness greater than or equal to about 0.001 µm and less than or equal to about 20 µm.

[0041] In one aspect, the precursor material may be disposed on or adjacent to the first surface of the conductive material layer to form a plurality of different precursor structures disposed in a predetermined pattern on the first surface of the conductive material layer.

[0042] In one aspect, at least a portion of each different precursor structure may be unobstructed by the electroactive material layer.

[0043] In one aspect, at least a portion of each different precursor structure may extend through the electroactive material layer.

[0044] In one aspect, the precursor material may include one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), perfluoroorganosiloxanes, and combinations thereof.

[0045] In one aspect, the solid electrolyte interface layer may comprise one or more materials selected from the group consisting of lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefins, hemicarbonates, and combinations thereof.

[0046] Other applicable areas will become apparent from the description provided herein. The descriptions and specific examples in this overview are intended to be illustrative only and are not intended to limit the scope of this disclosure. Attached Figure Description

[0047] The accompanying drawings described herein are for illustrative purposes only, and not for all possible implementations, and are not intended to limit the scope of this disclosure.

[0048] Figure 1 This is a schematic diagram of an exemplary electrochemical battery pack;

[0049] Figure 2A This is an exemplary electrode assembly (for example) comprising a current collector and a plurality of precursor structures disposed on the surface of the current collector, according to various aspects of this disclosure. Figure 1 The cross-sectional view of the battery pack shown in the figure shows a precursor structure extending through the electroactive material layer to form connection points for the solid electrolyte interface layer.

[0050] Figure 2B This is a cross-sectional view of an exemplary electrode according to various aspects of this disclosure, the electrode including a current collector, a plurality of surface structures disposed on the surface of the current collector, and a solid electrolyte interface layer connected to the current collector through the plurality of surface structures, wherein the surface structures are connected through the precursor structure (such as...) Figure 2A (As shown) reacts with lithium to form;

[0051] Figure 2C This is a plan view of an exemplary current collector including multiple surface structures according to various aspects of this disclosure;

[0052] Figure 2D This is a plan view of another exemplary current collector including multiple surface structures according to various aspects of this disclosure;

[0053] Figure 2E This is yet another exemplary plan view of a current collector including multiple surface structures according to various aspects of this disclosure; and

[0054] Figure 3This is a cross-sectional view of an exemplary electrode according to various aspects of the present disclosure, the electrode including a connecting intermediate layer between a current collector and parallel surfaces of an electroactive material layer, wherein the connecting intermediate layer facilitates bonding with a solid electrolyte interface layer disposed on an exposed surface of the electroactive material layer or disposed at an exposed surface of the electroactive material layer.

[0055] Throughout the several views in the accompanying figures, the corresponding figure labels indicate the corresponding parts. Detailed Implementation

[0056] Exemplary embodiments are provided so that this disclosure will be thorough and will fully communicate its scope to those skilled in the art. Numerous specific details, such as examples of specific compositions, components, apparatuses, and methods, are set forth to provide a full understanding of embodiments of this disclosure. It will be apparent to those skilled in the art that specific details are not required, that exemplary embodiments may be embodied in many different forms, and that none of them should be considered as limiting the scope of this disclosure. In some exemplary embodiments, well-known methods, well-known apparatus structures, and well-known techniques are not described in detail.

[0057] The terminology used herein is for the purpose of describing particular exemplary embodiments only and is not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "a," "an," and "the" as used herein are intended to include the plural forms as well. The terms "comprising," "including," "containing," and "having" are inclusive and thus describe the presence of the described features, elements, compositions, steps, integers, operations, and / or components, but do not exclude the presence or inclusion of one or more other features, integers, steps, operations, elements, components, and / or sets thereof. Although the open-ended term "comprising" should be understood as a non-limiting term used to describe and claim the various embodiments described herein, in some aspects it may instead be understood as a more restrictive and limiting term, such as "consisting of" or "essentially composed of." Thus, for any given embodiment describing a composition, material, component, element, feature, integer, operation, and / or process step, this disclosure also particularly includes embodiments consisting of or substantially consisting of such compositions, materials, components, elements, features, integers, operations, and / or process steps. In the case of "consisting of...", the alternative embodiments exclude any additional compositions, materials, components, elements, features, integers, operations, and / or process steps. In the case of "essentially composed of...", any additional compositions, materials, components, elements, features, integers, operations, and / or process steps that substantially affect the essential and novel characteristics are excluded from such embodiments. However, any compositions, materials, components, elements, features, integers, operations, and / or process steps that do not substantially affect the essential and novel characteristics may be included in the embodiments.

[0058] Any methods, procedures, and operations described herein should not be construed as necessarily requiring them to be performed in the specific order discussed or shown, unless explicitly stated otherwise. It should also be understood that additional or alternative steps may be used unless otherwise stated.

[0059] When a component, element, or layer is mentioned as being "on," "engaged," "connected," or "coupled" to another component or layer, it may be directly on, engaged, connected, or coupled to the other component, element, or layer, or there may be intermediate elements or layers. Conversely, when an element is mentioned as being directly on, "directly engaged," "directly connected," or "directly coupled" to another component or layer, there may be no intermediate elements or layers. Other terms used to describe relationships between elements should be interpreted in a similar manner (e.g., "between" vs. "directly between," "adjacent" vs. "directly adjacent," etc.). As used herein, the term "and / or" includes any and all combinations of one or more of the related enumerations.

[0060] Although the terms first, second, third, etc., may be used herein to describe various steps, elements, components, regions, layers, and / or sections, these steps, elements, components, regions, layers, and / or sections should not be limited by these terms unless otherwise specified. These terms may be used only to distinguish one step, element, component, region, layer, or section from another. Unless clearly indicated by the context, terms such as "first," "second," and other numerical terms used herein do not imply order or sequence. Therefore, the first step, element, component, region, layer, or section discussed below may be referred to as the second step, element, component, region, layer, or section without departing from the teachings of the exemplary embodiments.

[0061] For ease of description, spatial or temporal relative terms such as "before," "after," "inside," "outside," "below," "below," "lower," "upper," "upper," etc., may be used herein to describe the relationship of one element or feature relative to other elements or features shown in the figures. Spatial or temporal relative terms may be intended to include different orientations of the device or system in use or operation other than those shown in the figures.

[0062] Throughout this disclosure, numerical values ​​represent approximate measurements or range limits to include slight deviations from a given value and embodiments that substantially have the listed value as well as embodiments that precisely have the listed value. Except for the embodiments provided at the end of the Detailed Description section, all numerical values ​​of parameters (e.g., quantities or conditions) in this specification (including the appended claims) should be understood to be modified in all cases by the term "about," regardless of whether "about" actually appears before the numerical value. "About" means that the numerical value allows for a certain degree of slight inaccuracy (somewhat close to the exact value; substantially or reasonably close to the value; almost). If the inaccuracy provided by "about" is not understood in this ordinary sense in the art, then "about" as used herein refers at least to variations that may result from common methods of measuring and using such parameters. For example, "about" may include variations of less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to 0.5%, and in some respects optionally less than or equal to 0.1%.

[0063] In addition, the disclosure of the range includes all values ​​across the entire range and the disclosure of further subdivisions of the range, including the endpoints and subranges given for these ranges.

[0064] Exemplary embodiments will now be described more fully with reference to the accompanying drawings.

[0065] A typical lithium-ion battery pack (e.g., an electrochemical cell for cycling lithium ions) includes a first electrode (e.g., a positive electrode or cathode), an opposing second electrode (e.g., a negative electrode or anode), and a separator and / or electrolyte disposed between them. Typically, in a lithium-ion battery pack, the battery pack or cells can be electrically connected in a stacked or wound configuration to improve overall output. A lithium-ion battery pack operates by reversibly transferring lithium ions between the first and second electrodes. For example, during charging, lithium ions can move from the positive electrode to the negative electrode and in the opposite direction during discharging. The electrolyte is adapted to conduct lithium ions (or sodium ions in the case of a sodium-ion battery pack, etc.) and can be in liquid, gel, or solid form. For example, in… Figure 1 The image shows exemplary and schematic illustrations of an electrochemical cell (also known as a battery pack) 20.

[0066] Such batteries are used in transportation or automotive applications (e.g., motorcycles, boats, tractors, buses, mobile homes, campers, and tanks). However, the technology of this application can be used in a wide variety of other industries and applications, including, as non-limiting examples, aerospace components, consumer products, devices, buildings (e.g., houses, offices, sheds, and warehouses), office equipment and furniture, as well as industrial equipment machinery, agricultural or farm equipment, or heavy machinery. Furthermore, although the examples shown include a single cathode and a single anode, those skilled in the art will recognize that the teachings of this application extend to a wide variety of other configurations, including those having one or more cathodes and one or more anodes, and various current collectors (having an electroactive layer disposed on or adjacent to one or more of their surfaces).

[0067] Battery pack 20 includes a negative electrode assembly 52 (e.g., anode), a positive electrode assembly 54 (e.g., cathode), and a separator 26 disposed between the negative electrode assembly 52 and the positive electrode assembly 54. The negative electrode assembly 52 may include a current collector 32 and a negative electrode active material layer 22. The positive electrode assembly 54 may include a current collector 34 and a positive electrode active material layer 24. The separator 26 provides electrical isolation between the negative electrode active material layer 22 and the positive electrode active material layer 24—preventing physical contact. During lithium-ion cycling, the separator 26 also provides a path of least resistance for the internal passage of lithium ions (and in some cases, associated anions). In various aspects, the separator 26 includes an electrolyte 30, which may also be present in both the negative electrode active material layer 22 and the positive electrode active material layer 24. In some variations, the separator 26 may be a solid electrolyte. For example, the separator 26 may be defined by a plurality of solid electrolyte particles (not shown).

[0068] The negative electrode current collector 32 may be located at or near the negative electrode active material layer 22. The negative electrode current collector 32 may be a metal foil, metal grid or screen, or expanded metal, comprising copper or any other suitable conductive material known to those skilled in the art. The positive electrode current collector 34 may be located at or near the positive electrode active material layer 24. The positive electrode current collector 34 may be a metal foil, metal grid or screen, or expanded metal, comprising aluminum or any other suitable conductive material known to those skilled in the art. The negative electrode current collector 32 and the positive electrode current collector 34 respectively collect and move free electrons to and from the external circuit 40. For example, the interruptible external circuit 40 and the load device 42 may connect the negative electrode assembly 52 (via the negative electrode current collector 32) and the positive electrode assembly 54 (via the positive electrode current collector 34).

[0069] The battery pack 20 can generate current during discharge through a reversible electrochemical reaction that occurs when the external circuit 40 is closed (to connect the negative electrode assembly 52 and the positive electrode assembly 54) and the negative electrode active material layer 22 has a lower potential than the positive electrode active material layer 24. The potential difference between the positive and negative electrode active material layers 24 and 22 will drive electrons generated at the negative electrode assembly 52 by a reaction (e.g., oxidation of intercalated lithium) through the external circuit 40 to the positive electrode assembly 54. Similarly, lithium ions generated at the negative electrode assembly 52 will simultaneously transfer to the positive electrode assembly 54 through the electrolyte 30 contained in the separator 26. Electrons flow through the external circuit 40 and lithium ions migrate through the separator 26 containing the electrolyte 30 to form intercalated lithium at the positive electrode assembly 54. As mentioned above, the electrolyte 30 is also typically present in both the negative electrode assembly 52 and the positive electrode assembly 54. The current through the external circuit 40 can be controlled and directed through the load device 42 until the lithium in the negative electrode assembly 52 is depleted and the capacity of the battery pack 20 is reduced.

[0070] The lithium-ion battery pack 20 can be charged or recharged at any time by connecting an external power source to it to reverse the electrochemical reactions that occur during battery pack discharge. Connecting an external electrical energy source to the battery pack 20 promotes a reaction at the positive electrode 24, such as the non-spontaneous oxidation of intercalated lithium, resulting in the generation of electrons and lithium ions. The lithium ions flow back through the electrolyte 30 and the separator 26 to the negative electrode assembly 52 to replenish the negative electrode assembly 52 with lithium (e.g., intercalated lithium, lithium metal, or lithium metal alloy) for use in the next battery pack discharge event. Thus, a complete discharge event followed by a complete charge event is considered a cycle in which lithium ions circulate between the positive electrode assembly 54 and the negative electrode assembly 52. ​​The external power source that can be used to charge the battery pack 20 may vary depending on the size, construction, and specific end use of the battery pack 20. Some notable and exemplary external power sources include, but are not limited to, AC-DC converters and vehicle alternators connected to the AC grid via a wall socket.

[0071] In many lithium-ion battery pack configurations, each of the negative electrode current collector 32, the negative electrode active material layer 22, the separator 26, the positive electrode active material layer 24, and the positive electrode current collector 34 is fabricated as a relatively thin layer (e.g., from a few micrometers to a fraction of a millimeter or less) and the layers are connected in an electrically parallel arrangement to provide suitable energy and power encapsulation. In various aspects, the battery pack 20 may also include a variety of other components, although not depicted herein, that are known to those skilled in the art. For example, the battery pack 20 may include a housing, gaskets, end caps, tabs, battery pack terminals, and any other conventional components or materials that may be located within or around the battery pack 20 (including between or around the negative electrode assembly 52, the positive electrode assembly 54, and / or the separator 26). Figure 1 The battery pack 20 shown includes a liquid electrolyte 30 and illustrates a representative concept of battery pack operation. However, this technology is also applicable to solid-state battery packs that include solid electrolytes and / or solid electroactive particles, which can have different designs as known to those skilled in the art.

[0072] As described above, the size and shape of the battery pack 20 can vary depending on the specific application it is designed for. Battery-powered vehicles and handheld consumer electronics are two examples of where the battery pack 20 is most likely to be designed with different sizes, capacities, and power output specifications. The battery pack 20 can also be connected in series or parallel with other similar lithium-ion batteries or battery packs to generate greater voltage output, energy, and power (if required by the load device 42). Thus, the battery pack 20 can generate current to the load device 42, which is part of the external circuit 40. The load device 42 can be powered by the current flowing through the external circuit 40 when the battery pack 20 discharges. While the electrical load device 42 can be any number of known electrically driven devices, some specific examples include electric motors for electric vehicles, laptops, tablets, mobile phones, and cordless power tools or appliances. The load device 42 can also be a power generation device that charges the battery pack 20 to store electrical energy.

[0073] Re-reference Figure 1The positive electrode assembly 54, the negative electrode assembly 52, and the separator 26 may each contain an electrolyte solution or system 30 within their pores that can conduct lithium ions (or sodium ions, potassium ions, magnesium ions, etc.) between the negative electrode assembly 52 and the positive electrode assembly 54. Any suitable electrolyte 30 capable of conducting lithium ions between the negative electrode assembly 52 and the positive electrode assembly 54, whether in solid, liquid, or gel form, can be used in the lithium-ion battery pack 20. In some aspects, the electrolyte 30 may be a non-aqueous liquid electrolyte solution (e.g., >1M) containing a lithium salt dissolved in an organic solvent or mixture of organic solvents. In some cases, the electrolyte 30 may also contain one or more additives, such as vinylene carbonate (VC), butylene carbonate (BC), fluoroethylene carbonate (FEC), etc. Many conventional non-aqueous liquid electrolyte solutions 30 can be used in the lithium-ion battery pack 20.

[0074] In some aspects, electrolyte 30 may be a non-aqueous liquid electrolyte solution comprising one or more lithium salts dissolved in an organic solvent or a mixture of organic solvents. The lithium salt may comprise one or more cations coupled to one or more anions. The cation may be selected from Li... + Na + K + Al 3+ Mg 2+ The anion may be selected from PF. 6- BF 4- TFSI - FSI - CF3SO3 - (C2F5S2O2)N - For example, a non-limiting list of lithium salts that can be dissolved in organic solvents to form non-aqueous liquid electrolyte solutions includes lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalate)borate (LiB(C2O4)2) (LiBOB), lithium difluorooxalateborate (LiBF2(C2O4)), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethane)sulfonylimide (LiN(CF3SO2)2), lithium bis(fluorosulfonylimide) (LiN(FSO2)2) (LiSFI), and combinations thereof.

[0075] These and other similar lithium salts are soluble in a variety of non-aqueous, aprotic organic solvents, including but not limited to various alkyl carbonate esters, such as cyclic carbonates (e.g., ethylene carbonate (EC), propylene carbonate (PC), butyl carbonate (BC), fluoroethylene carbonate (FEC)), linear carbonates (e.g., dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC)), aliphatic carboxylic acid esters (e.g., methyl formate, methyl acetate, methyl propionate), γ-lactones (e.g., γ-butyrolactone, γ-valerolactone), chain ethers (e.g., 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g., tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane), sulfur compounds (e.g., sulfolane), and combinations thereof.

[0076] In some cases, the porous separator 26 may comprise a microporous polymer separator containing a polyolefin. The polyolefin may be a homopolymer (derived from a single monomer component) or a hybrid (derived from more than one monomer component), and may be linear or branched. If the hybrid is derived from two monomer components, the polyolefin may exhibit any copolymer chain arrangement, including those of block copolymers or random copolymers. Similarly, if the polyolefin is a hybrid derived from more than two monomer components, it may also be a block copolymer or a random copolymer. In some aspects, the polyolefin may be polyethylene (PE), polypropylene (PP), or a blend of polyethylene (PE) and polypropylene (PP), or a multilayer structured porous membrane of PE and / or PP. Commercially available polyolefin porous separator membranes 26 include CELGARD, available from Celgard LLC. ® 2500 (a single-layer polypropylene spacer) and CELGARD ® 2320 (A three-layer polypropylene / polyethylene / polypropylene separator).

[0077] In some aspects, the spacer 26 may further include one or more of a ceramic coating and a heat-resistant material coating. The ceramic coating and / or heat-resistant material coating may be disposed on one or more sides of the spacer 26. The material forming the ceramic layer may be selected from: alumina (Al2O3), silicon dioxide (SiO2), and combinations thereof. The heat-resistant material may be selected from: Nomex, Aramid, and combinations thereof.

[0078] When the spacer 26 is a microporous polymer spacer, it can be a single-layer or multi-layer laminated material, manufactured by dry or wet processes. For example, in some cases, a single layer of the polyolefin can form the entire spacer 26. In other aspects, the spacer 26 can be a fibrous membrane having a large number of pores extending between opposing surfaces and can have an average thickness of, for example, less than 1 mm. However, as another example, multiple discrete layers of the same or different polyolefins can be assembled to form the microporous polymer spacer 26. The spacer 26 may also contain other polymers besides the polyolefin, such as, but not limited to, polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyamide, polyimide, poly(amide-imide) copolymer, polyetherimide, and / or cellulose, or any other material suitable for producing the desired porous structure. The polyolefin layer and any other optional polymer layer may be further included in the spacer 26 as a fibrous layer to help provide the spacer 26 with suitable structural and porosity characteristics. In some aspects, the spacer 26 may also be mixed with a ceramic material, or its surface may be coated with a ceramic material. For example, the ceramic coating may comprise alumina (Al2O3), silicon dioxide (SiO2), titanium dioxide (TiO2), or a combination thereof. Various conventionally available polymers and commercial products for forming the spacer 26 are considered, as well as many manufacturing methods that can be used to produce such a microporous polymer spacer 26. The spacer 26 may have a thickness greater than or equal to about 1 µm to less than or equal to about 50 µm, and in some cases, optionally greater than or equal to about 1 µm to less than or equal to about 20 µm.

[0079] In all aspects, a solid electrolyte ("SSE") (not shown) used as both the electrolyte and the separator can be substituted. Figure 1 The solid electrolyte comprises a porous separator 26 and an electrolyte 30 disposed within the porous separator 26. The solid electrolyte may be disposed between the positive electrode assembly 54 and the negative electrode assembly 52, for example, between the positive electrode active material layer 24 and the negative electrode active material layer 22. The solid electrolyte facilitates lithium-ion transfer while providing mechanical isolation and electrical insulation between the negative electrode assembly 52 and the positive electrode assembly 24. As a non-limiting example, the solid electrolyte may comprise multiple solid electrolyte particles, such as LiTi2(PO4)3, LiGe2(PO4)3, and Li7La3Zr2O. 12 Li3xLa 2 / 3 -xTiO3, Li3PO4, Li3N, Li4GeS4, Li 10 GeP2S 12 , Li2S-P2S5, Li6PS5Cl, Li6PS5Br, Li6PS5I, Li3OCl, Li 2.99 Ba0.005 ClO or a combination thereof. The solid electrolyte particles may be nanoscale oxide-based solid electrolyte particles. In other variations, a gel electrolyte may be used instead. Figure 1 The porous separator 26 and electrolyte 30 are included.

[0080] The positive electrode assembly 54 may include a current collector 34 and a positive electrode active material layer 24. The positive electrode active material layer 24 may be formed of a lithium-based active material (or a sodium-based active material in the case of a sodium-ion battery pack, or a potassium-based active material in the case of a potassium-ion battery pack, or a magnesium-based active material in the case of a magnesium-ion battery pack, etc.), which is capable of lithium intercalation and deintercalation, alloying and dealloying, conversion reactions, or plating and peeling, while serving as the positive terminal of the battery pack 20. For example, the positive electrode active material layer 24 may be defined by a plurality of active material particles (not shown) arranged in one or more layers to define the three-dimensional structure of the positive electrode active material layer 24. An electrolyte 30 may be introduced, for example, after battery assembly and contained within the pores (not shown) of the positive electrode active material layer 24. In some variations, the positive electrode active material layer 24 may include a plurality of electrolyte particles (not shown). In each case, the positive electrode active material layer 24 (including one or more layers) may have a thickness greater than or equal to about 1 µm to less than or equal to about 1,000 µm.

[0081] A known, exemplary, common class of electroactive materials that can be used to form the positive electrode active material layer 24 is layered lithium transition metal oxides. For example, in some aspects, the positive electrode active material layer 24 may comprise one or more materials having a spinel structure, such as lithium manganese oxide (Li). (1+x) Mn₂O₄, where 0.1≤x≤1), lithium manganese nickel oxide (LiMn (2-x) Ni x O4, where 0 ≤ x ≤ 0.5 (e.g., LiMn) 1.5 Ni 0.5 O4); one or more materials having a layered structure, such as lithium cobalt oxide (LiCoO2), lithium nickel manganese cobalt oxide (Li(Ni)O2), etc. x Mn y Co z O2, where 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1 (e.g., LiMn) 0.33 Ni 0.33 Co 0.33 O2), or lithium nickel cobalt metal oxide (LiNi) (1-x-y) Co x M yO2, where 0 < x < 0.2, y < 0.2, and M can be Al, Mg, Ti, etc.); or a lithium iron polyanion oxide having an olivine structure, such as lithium iron phosphate (LiFePO4), lithium manganese iron phosphate (LiMn 2-x Fe x PO4, where 0 < x < 0.5), or lithium iron fluorophosphate (Li2FePO4F).

[0082] In some other aspects, the positive electrode electroactive material layer 24 can include one or more high-voltage oxides (such as LiNi 0.5 Mn 1.5 O4, LiCoPO4), one or more rock salt layered oxides (such as LiCoO2, LiNi x Mn y Co 1-x-y O2 (where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1), LiNi x CO y Al 1-x-y O2 (where 0 ≤ x ≤ 1, 0 ≤ y ≤ 1), LiNi x Mn 1-x O2 (where 0 ≤ x ≤ 1), Li 1+x MO2 (where 0 ≤ x ≤ 2 and where M refers to a metal element selected from Mn, Ni, Co, etc.), one or more polyanions (such as LiV2(PO4)3), and other similar lithium transition metal oxides. The positive electrode electroactive material can also be surface-coated and / or doped. For example, the positive electrode electroactive material can include LiNbO3-coated LiNi 0.5 Mn 1.5 O4.

[0083] In each case, the positive electrode electroactive material can optionally be mixed with an electron conduction material that provides an electron conduction path and / or at least one polymer binder material that improves the electrode structure integrity. For example, the positive electrode electroactive material and the electron conduction or conductive material can be slurry cast with such a binder, such as polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber, or carboxymethyl cellulose (CMC), nitrile rubber (NBR), styrene-butadiene rubber (SBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, or lithium alginate. The conductive material can include carbon-based materials, powdered nickel or other metal particles, or conductive polymers. The carbon-based materials can include, for example, graphite, acetylene black (such as KETCHEN TM black or DENKA TM black or SuperP TMParticles such as carbon fibers and nanotubes, graphene, and graphene oxide. Examples of conductive polymers include polyaniline, polythiophene, polyacetylene, and polypyrrole. In some applications, mixtures of conductive materials may be used.

[0084] For example, the positive electrode active material layer 24 may comprise more than or equal to about 30% by weight to less than or equal to about 98% by weight, and in some aspects optionally more than or equal to about 50% by weight to less than or equal to about 95% by weight of the positive electrode active material; more than or equal to about 0% by weight to less than or equal to about 30% by weight, and in some aspects optionally more than or equal to about 5% by weight to less than or equal to about 20% by weight of one or more conductive materials; and more than or equal to about 0% by weight to less than or equal to about 20% by weight, and in some aspects optionally more than or equal to about 5% by weight to less than or equal to about 15% by weight of one or more adhesives.

[0085] The negative electrode assembly 54 may include a current collector 32 and a negative electrode active material layer 22. The negative electrode active material layer 22 may be formed of a lithium host material (or a sodium host material in the case of a sodium-ion battery pack, or a potassium host material in the case of a potassium-ion battery pack, or a magnesium host material in the case of a magnesium-ion battery pack, etc.) capable of being used as the negative terminal of a battery pack. For example, the negative electrode active material layer 22 may contain a lithium host material (e.g., a negative electrode active material) capable of being used as the negative terminal of a battery pack 20. In various aspects, the negative electrode active material layer 22 may be defined by a plurality of negative electrode active material particles (not shown). Such negative electrode active material particles may be disposed in one or more layers to define the three-dimensional structure of the negative electrode active material layer 22. The electrolyte 30 may be introduced, for example, after battery assembly and contained within the pores (not shown) of the negative electrode active material layer 22. In some variations, the negative electrode active material layer 22 may include a plurality of electrolyte particles (not shown). The negative electrode electroactive material layer 22 (including one or more layers) may have a thickness greater than or equal to about 1 µm to less than or equal to about 2,000 µm, and in some respects, optionally greater than or equal to about 10 µm to less than or equal to about 1,000 µm.

[0086] The negative electrode active material layer 22 may include a lithium-containing negative electrode active material, such as lithium metal. In some variations, the negative electrode active material layer 22 may be a film or layer formed of lithium metal or a lithium metal alloy. Other materials may also be used, for example, in some variations combined with lithium metal and / or lithium metal alloys to form the negative electrode, including, for example, other metallic materials such as magnesium (Mg), sodium (Na), potassium (K), calcium (Ca), etc. In some variations, further other materials may be used, for example, in some variations combined with lithium metal and / or lithium metal alloys to form the negative electrode active material layer 22, including, for example, carbonaceous materials (e.g., graphite, hard carbon, soft carbon) and / or lithium-silicon, silicon-containing binary and ternary alloys, and / or tin-containing alloys (e.g., Si, Li-Si, SiO). x (where 0≤x≤2), Si-Sn, SiSnFe, SiSnAl, SiFeCo, SnO2, etc.). For example, in some variations, the negative electrode active material layer 22 can be a silicon-based anode. Such a silicon-based anode can have a thickness of less than or equal to about 10µm.

[0087] In each case, the negative electrode active material in the negative electrode active material layer 22 may optionally be mixed with one or more conductive materials that provide an electron conduction path and / or at least one polymeric binder material that improves the structural integrity of the negative electrode 22. For example, the negative electrode active material in the negative electrode 22 may optionally be mixed with a binder such as polyimide, polyamic acid, polyamide, polysulfone, polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber, or carboxymethyl cellulose (CMC), nitrile rubber (NBR), styrene-butadiene rubber (SBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, or lithium alginate. The conductive material may include carbon-based materials, powdered nickel or other metal particles, or conductive polymers. Carbon-based materials may include, for example, graphite, acetylene black (e.g., KETCHEN). TM Black or Denka TM Particles such as black carbon fibers and nanotubes, graphene, etc. Examples of conductive polymers include polyaniline, polythiophene, polyacetylene, polypyrrole, etc. In some applications, mixtures of conductive materials can be used.

[0088] The negative electrode electroactive material layer 22 may comprise more than or equal to about 10% by weight and less than or equal to about 99% by weight of the electroactive material, more than or equal to about 0% by weight and less than or equal to about 20% by weight of the electronically conductive material, and more than or equal to about 0% by weight and less than or equal to about 20% by weight, and in some aspects optionally more than or equal to about 1% by weight and less than or equal to about 20% by weight of the at least one polymer binder. In some variations, the negative electrode 22 may also comprise more than or equal to about 0% by weight and less than or equal to about 89% by weight of graphite active material.

[0089] In various aspects, the solid electrolyte interface (SEI) layer can be in the negative electrode electroactive material layer (e.g., as shown in the figure). Figure 1 The negative electrode active material layer 22 shown), or the positive electrode active material layer (e.g., as shown) Figure 1 The positive electrode electroactive material layer 24 shown), and the separator and / or electrolyte (e.g., as shown) Figure 1 The solid electrolyte interface layer is formed on or between the separator 20 and / or electrolyte 30 shown. In each case, the solid electrolyte interface layer can provide protection for the negative electrode active material layer and / or the positive electrode active material layer. However, when the solid electrolyte interface layer becomes too thick or physically degrades, it can become detrimental to battery performance. Solid electrolyte interface layers often lead to continuous electrolyte consumption and lithium-ion loss, which can result in irreversible capacity decay in lithium-ion battery packs. For example, any cracking or bending in the solid electrolyte interface layer during cycling can cause the solid electrolyte interface layer to reform, for example at the new interface, which leads to additional electrolyte and lithium consumption.

[0090] According to various aspects, this disclosure provides a method for advantageously controlling the electroactive material layer (e.g., as shown in the figure) in the negative electrode layer. Figure 1 The negative electrode active material layer 22 shown), or the positive electrode active material layer (e.g., as shown) Figure 1 The positive electrode electroactive material layer 24 shown), and the separator and / or electrolyte (e.g., as shown) Figure 1 The manner in which the solid electrolyte interface layer is formed between the separator 20 and / or the electrolyte 30 shown. For example, Figure 2A The illustration shows a current collector 132 with a negative electrode (e.g., as shown in the figure). Figure 1 An exemplary negative electrode assembly 100 of the negative electrode current collector 132 shown in the figure includes a plurality of different precursor structures 140 configured to form connection points (e.g., fixing points) for a solid electrolyte interface layer 150, whether the solid electrolyte interface layer 150 is formed in situ or formed as an artificial protective layer.

[0091] As shown, each of the different precursor structures 140 may extend at least partially through at least a portion of the electroactive material layer 122. The precursor structure 140 may have an average height or thickness greater than or equal to about 20% and less than or equal to about 400% higher than the average charged height or thickness of the electroactive material layer 122. For example, the electroactive material layer 122 may have an initial height or thickness greater than or equal to about 10 µm and less than or equal to about 200 µm, and the precursor structure 140 may have an average height or thickness greater than or equal to about 1 µm and less than or equal to about 500 µm, and in some aspects, optionally greater than or equal to about 5 µm and less than or equal to about 500 µm. In each case, at least a portion of each of the precursor structures 140 is freely available for forming a connection with the solid electrolyte interface layer 150. In some variations, as shown, a portion of the precursor structure 140 may extend partially beyond the exposed surface of the electroactive material layer 122.

[0092] The precursor structure 140 can be formed using a material with little or no conductivity compared to the current collector 132. For example, the material forming the precursor structure 140 can have an ionic conductivity less than that of the electrolyte. At typical battery pack operating temperatures, the non-conductive material can have an ionic conductivity less than about 10. -4 S / cm, and in some respects optionally less than about 10 -5 The ionic conductivity is S / cm. Limiting the conductivity of the precursor structure 140 helps prevent it from detaching from the current collector 132, while providing a strong bond with the solid electrolyte interface layer 150 to prevent mechanical stripping during cycling. In various aspects, the precursor structure 140 may comprise fluoride-containing materials capable of producing lithium fluoride (LiF) as a decomposition product upon reaction with lithium metal. For example, the surface structure 140 may comprise polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), or perfluoroorganosiloxanes.

[0093] In each case, such as Figure 2B As shown, the precursor structure 140 can form a chemical bond with the solid electrolyte interface layer 150. For example, a reaction can occur between the negative electrode material (e.g., lithium material) forming the electroactive material layer 122 and the precursor structure 140 (e.g., polyvinylidene fluoride (PVdF)) to form lithium fluoride and other decomposition products (i.e., reaction byproducts), which form the surface structure 142 connecting the current collector 132 and the solid electrolyte interface layer 150.

[0094] Chemical bonding (i.e., surface structure 142) can restrict the free movement (e.g., flexure) of the solid electrolyte interface layer 150. By restricting the movement of the solid electrolyte interface layer 150, surface structure 142 provides a mechanical means to control the growth and microstructure of the solid electrolyte interface layer 150 on the electroactive material layer 122 (e.g., lithium metal) or at the interface between the electroactive material layer 122 and the separator and / or electrolyte (not shown), without the use of additives and alteration of cycle rate. For example, surface structure 142 can help reduce or prevent premature breakage or degradation of the solid electrolyte interface layer 150. More specifically, the location of the precursor structure 140 and thus the resulting surface structure 142 can be selected to selectively create areas of lithium plating or stripping and / or to control other thermal and mechanical properties during cycling by creating structures with thermal conductivity and mechanical stiffness different from those of surface structure 142 (e.g., lithium channels, rings, circles, or other shapes).

[0095] The solid electrolyte interface layer 150 may be a substantially continuous coating or layer. For example, the solid electrolyte interface layer 150 may cover more than or equal to about 90%, optionally more than or equal to about 92%, optionally more than or equal to about 95%, optionally more than or equal to about 97%, optionally more than or equal to about 98%, optionally more than or equal to about 99%, or in some respects, optionally more than or equal to about 99.5%. The solid electrolyte interface layer 150 may have an average height or thickness of more than or equal to about 0.1 µm and less than or equal to about 400 µm.

[0096] The solid electrolyte interface layer 150 may comprise, for example, lithium carbonate (Li₂CO₃), lithium peroxide (Li₂O₂), lithium hydroxide (LiOH), lithium oxide (Li₂O), lithium fluoride (LiF), lithium nitride (Li₃N), polyolefins, hemicarbonates, and other similar inorganic or organic compounds. In some variations, the solid electrolyte interface layer 150 is formed in situ, and its composition will depend on the selected battery pack materials (including, for example, electrolytes and additives) and the cycle and thermal history. In other variations, the solid electrolyte interface layer 150 may be an artificial protective layer applied to or adjacent to the exposed surfaces of the surface structure 140 and the electroactive material layer 122 prior to battery assembly.

[0097] like Figures 2C-2EAs shown, in various aspects, the precursor structure 140 and therefore the surface structure 142 can be of a generally circular cross-sectional shape. The precursor structure 140 can have a three-dimensional structure that is, for example, substantially cylindrical or, in some variations, fibrous. However, those skilled in the art will understand that the precursor structure 140 can take other forms in various aspects. By way of example only, in some variations, the precursor structure 140 can have other cross-sectional shapes, such as a generally elliptical shape, a generally triangular shape, a generally trapezoidal shape, a generally linear shape, a generally flap shape, etc.

[0098] The precursor structure 140 and therefore the surface structure 142 can form various patterns on the surface of the current collector 132. For example, such as Figure 2C As shown, in some variations, the precursor structure 140 may be configured to form a plurality of linear rows 134 on the surface 130 of the current collector 132. In other variations, such as Figure 2D As shown, the precursor structure 140 can be configured to form a plurality of narrow channels 136 on the surface 130 of the current collector 132. In other variations, such as Figure 2E As shown, the precursor structure 140 may be arranged in a spiral pattern on the surface 130 of the current collector 132. Those skilled in the art will understand that, although not specifically illustrated, the precursor structure 140 may be arranged on the surface 130 of the current collector 132 to form various other patterns. For example, in various aspects, the precursor structure 140 may form a grid, a channel group, a ring, or other mesoscale structures.

[0099] Patterns can be selected based on desired stripping or plating current density, stress or strain optimization, thermal conductivity or electrical conductivity control, etc. Creating different patterns can reduce the available area or volume, allowing for engineered methods to guide ion currents within the battery. For example, larger area or volume density can be formed in predetermined regions within the battery, such as... Figure 2DThe precursor structure 140 shown is positioned to form a plurality of narrow channels 136. Different patterns also allow for control of bending and / or heat flow during cycling by, for example, creating a set of zigzags or creating metal channels in locations where the battery pack may flex during operation to effectively guide heat flow in one direction. Furthermore, different patterns can allow for the creation of different regions suited to different operating conditions, including regions with improved robustness for, for example, fast charging. During fast charging, the kinetic constraints of the electrolyte or other components can determine how plating or stripping behavior is driven within the battery, and pattern designs can be selected to create partially, physically separated regions that can be used to guide current to desired areas within the battery. Those regions may have additional support for the solid electrolyte interface layer 150 to prevent degradation, thermal channels to control heat, or area and volume adjustments to adapt to the kinetics of the desired lithium plating configuration.

[0100] In each case, the precursor structure 140 may have an average spacing greater than or equal to about 0.1 µm to less than or equal to about 50 µm. The precursor structure 140 may cover more than or equal to about 1% to less than or equal to about 50% of the total surface area of ​​the current collector 132.

[0101] In other variations, such as Figure 3 As shown, an intermediate layer 240 may be disposed between the current collector 232 and the electroactive material layer 222. The intermediate layer 240 may be a substantially continuous layer or coating having a thickness greater than or equal to about 0.001 µm and less than or equal to about 20 µm, and covering a first surface of the current collector 232 of greater than or equal to about 90%, optionally greater than or equal to about 92%, optionally greater than or equal to about 95%, optionally greater than or equal to about 97%, optionally greater than or equal to about 98%, optionally greater than or equal to about 99%, or in some respects, optionally greater than or equal to about 99.5%.

[0102] Intermediate layer 240 may be a connecting layer for solid electrolyte interface layer 250, facilitated by the formation of lithium nucleation beneath solid electrolyte interface layer 250. In some variations, intermediate layer 240 may be a carbon coating. In other variations, intermediate layer 240 may be a physical nucleation site of a material that is sufficiently inert relative to lithium metal or other battery components. In still other variations, intermediate layer 240 may be a metallic coating, including, for example, platinum or gold. In each case, intermediate layer 240 may enable certain materials, such as fluorinated organic materials (e.g., perfluoroorganosiloxane precursors) and / or boron-containing organic materials, to adhere to the current collector and / or improve the plating of lithium metal onto or from the current collector.

[0103] In various aspects, this disclosure provides a method for forming multiple surface structures (e.g., on or at the surface of a current collector) on the surface of a current collector. Figures 2A-2E (as shown) and / or forming a bonding layer (e.g., as shown) on or at the surface of the current collector. Figure 3 The method shown in the figure; and a method for connecting a current collector and a solid electrolyte interface layer. In each case, the surface structure or connecting layer may be directly disposed on or adjacent to the surface of the current collector, for example, using only a vapor deposition process, a roll forming process, etc. In such cases, an electroactive material layer (e.g., lithium metal) may be disposed on or adjacent to the exposed surface of the current collector and / or the surface structure or connecting layer. For example, in some variations, a precursor of the surface structure or connecting layer may be disposed on or adjacent to the surface of the current collector, and the electroactive material layer may subsequently be disposed on or adjacent to the exposed surface of the current collector and / or the precursor, and the surface structure or connecting layer can be formed once the electroactive material layer and the precursor react.

[0104] Once the surface structure or bonding layer is formed, the solid electrolyte interface layer can be formed on or adjacent to the electroactive material layer (e.g., lithium metal), or at the interface between the electroactive material layer and the separator and / or electrolyte. In some variations, the solid electrolyte interface layer can be an artificial protective layer disposed on or adjacent to the surface structure or bonding layer, for example, using only vapor deposition, roll forming, etc. In other variations, the solid electrolyte interface layer can be a naturally occurring solid electrolyte interface layer formed during battery conditioning or cycling. In such cases, the battery may also include electrolyte additives (e.g., fluorinated materials) that facilitate the formation of a solid electrolyte interface layer with desired composition, density, etc.

[0105] The above description of the embodiments has been provided for illustration and description purposes. It is not intended to be exhaustive or limiting of this disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but are interchangeable and can be used in alternative embodiments where applicable, even if not explicitly shown or described. It can also be varied in many ways. Such variations are not considered to depart from this disclosure, and all such modifications are intended to be included within the scope of this disclosure.

[0106] This application may include the following technical solutions.

[0107] 1. An electrochemical battery comprising:

[0108] Conductive material layer;

[0109] Precursor material, the precursor material being disposed on or adjacent to the first surface of the conductive material layer, wherein the non-conductive material has a density of less than about 10. -4 Ionic conductivity in S / cm; and

[0110] An electroactive material layer is disposed on or adjacent to the precursor material.

[0111] 2. The electrochemical cell according to Scheme 1, wherein the precursor material is disposed on or adjacent to the first surface of the conductive material to form a substantially continuous layer having an average thickness greater than or equal to about 0.001 µm to less than or equal to about 20 µm.

[0112] 3. The electrochemical cell according to Scheme 1 further includes:

[0113] A solid electrolyte interface layer is disposed on or adjacent to the exposed surface of the electroactive material layer.

[0114] 4. The electrochemical battery according to Scheme 1, wherein the solid electrolyte interface layer comprises one or more materials selected from the following: lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefin, hemicarbonate, and combinations thereof.

[0115] 5. The electrochemical cell according to Scheme 1, wherein the precursor material is disposed on or adjacent to the first surface of the conductive material layer to form a plurality of different precursor structures disposed in a predetermined pattern on the first surface of the conductive material layer.

[0116] 6. The electrochemical cell according to Scheme 5, wherein at least a portion of each different precursor structure is not blocked by the electroactive material layer.

[0117] 7. The electrochemical cell according to Scheme 5, wherein at least a portion of each different precursor structure extends through the electroactive material layer.

[0118] 8. The electrochemical cell according to claim 5, wherein the total surface area of ​​the first surface of the conductive material layer covered by the different precursor structures is greater than or equal to about 1% and less than or equal to about 50%, and

[0119] The different precursor structures have an average spacing of about 0.1 µm to about 50 µm.

[0120] 9. The electrochemical battery according to Scheme 5, wherein the average height of each different precursor structure is greater than or equal to about 20% to less than or equal to about 400% higher than the average thickness of the electroactive material layer.

[0121] 10. The electrochemical cell according to Scheme 5, wherein the average height of each different precursor structure is greater than about 1 µm and less than or equal to about 500 µm, and

[0122] The electroactive material layer has an initial thickness of more than about 10 µm to less than or equal to about 200 µm.

[0123] 11. The electrochemical cell according to Scheme 5 further includes:

[0124] A solid electrolyte interface layer is disposed on or adjacent to the exposed surface of the electroactive material layer and in contact with each of the different precursor structures, wherein the different precursor structures are configured to form a surface structure that chemically bonds the solid electrolyte interface layer and the conductive material layer.

[0125] 12. The electrochemical battery according to claim 11, wherein the solid electrolyte interface layer comprises one or more materials selected from the group consisting of lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefin, hemicarbonate, and combinations thereof.

[0126] 13. The electrochemical battery according to Scheme 1, wherein the precursor material comprises one or more materials selected from the group consisting of polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), perfluoroorganosiloxanes, and combinations thereof.

[0127] 14. An electrochemical cell comprising:

[0128] Conductive material layer;

[0129] Multiple different precursor structures are arranged in a predetermined pattern on a first surface of the conductive material layer, wherein the different precursor structures cover a total surface area of ​​the first surface of the conductive material layer that is greater than or equal to about 1% and less than or equal to about 50%, and the different precursor structures have an average spacing of greater than or equal to about 0.1 µm and less than or equal to about 50 µm; and

[0130] An electroactive material layer is disposed on or adjacent to the precursor material, such that at least a portion of each different precursor structure is not obstructed by the electroactive material layer.

[0131] 15. The electrochemical cell according to claim 14, wherein at least a portion of each different precursor structure extends through the electroactive material layer.

[0132] 16. The electrochemical cell according to Scheme 14 further includes:

[0133] A solid electrolyte interface layer is disposed on or adjacent to the exposed surface of the electroactive material layer and in contact with each of the different precursor structures, wherein the different precursor structures are configured to form a surface structure that chemically bonds the solid electrolyte interface layer and the conductive material layer.

[0134] 17. The electrochemical battery according to claim 14, wherein the solid electrolyte interface layer comprises one or more materials selected from: lithium carbonate (Li₂CO₃), lithium peroxide (Li₂O₂), lithium hydroxide (LiOH), lithium oxide (Li₂O), lithium fluoride (LiF), lithium nitride (Li₃N), polyolefins, hemicarbonates, and combinations thereof; and

[0135] Each of the different precursor structures comprises one or more materials selected from the following: polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), perfluoroorganosiloxanes, and combinations thereof.

[0136] 18. An electrochemical cell comprising:

[0137] Conductive material layer;

[0138] An electroactive material layer is disposed on the exposed surface of the conductive material layer or adjacent to it;

[0139] A solid electrolyte interface layer, wherein the solid electrolyte interface layer is disposed on or adjacent to the exposed surface of the electroactive material layer; and

[0140] Multiple different surface structures are freely obtainable through the electroactive material layer and chemically bonded to the first surface of the conductive material layer and the solid electrolyte interface layer.

[0141] 19. The electrochemical battery according to claim 18, wherein the plurality of surface structures comprise lithium fluoride (LiF), and

[0142] The solid electrolyte interface layer comprises one or more materials selected from the following: lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefins, hemicarbonates, and combinations thereof.

[0143] 20. The electrochemical cell according to claim 18, wherein the total surface area of ​​the first surface covering the conductive material layer by the different surface structures is greater than or equal to about 1% and less than or equal to about 50%, and

[0144] The different surface structures have an average spacing of about 0.1 µm to about 50 µm.

Claims

1. An electrochemical battery, comprising: Conductive material layer; Precursor materials are disposed on a first surface of the conductive material layer to form a plurality of different precursor structures disposed on the first surface of the conductive material layer in a predetermined pattern, wherein the non-conductive precursor materials have a density of less than 10. -4 Ionic conductivity in S / cm; An electroactive material layer is disposed on the precursor material; and A solid electrolyte interface layer is disposed on the exposed surface of the electroactive material layer and contacts each of the different precursor structures, wherein the different precursor structures are configured to form a surface structure that chemically connects the solid electrolyte interface layer and the conductive material layer.

2. The electrochemical cell according to claim 1, wherein the precursor material is disposed on the first surface of the conductive material to form a continuous layer having an average thickness of 0.001 µm to 20 µm or less.

3. The electrochemical battery according to claim 1, further comprising: A solid electrolyte interface layer is disposed on the exposed surface of the electroactive material layer.

4. The electrochemical battery according to claim 1, wherein the solid electrolyte interface layer comprises one or more materials selected from the following: lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefin, and hemicarbonate.

5. The electrochemical battery of claim 1, wherein at least a portion of each different precursor structure is not blocked by the electroactive material layer.

6. The electrochemical cell of claim 1, wherein at least a portion of each different precursor structure extends through the electroactive material layer.

7. The electrochemical cell of claim 1, wherein the total surface area of ​​the first surface of the conductive material layer covered by the different precursor structures is greater than or equal to 1% and less than or equal to 50%, and The different precursor structures have an average spacing of 0.1 µm to 50 µm.

8. The electrochemical battery of claim 1, wherein the average height of each different precursor structure is greater than or equal to 20% and less than or equal to 400% higher than the average thickness of the electroactive material layer.

9. The electrochemical cell according to claim 1, wherein the average height of each different precursor structure is greater than 1 µm and less than or equal to 500 µm, and The electroactive material layer has an initial thickness of greater than 10µm to less than or equal to 200µm.

10. The electrochemical battery according to claim 1, wherein the solid electrolyte interface layer comprises one or more materials selected from the following: lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefin, and hemicarbonate.

11. The electrochemical battery according to claim 1, wherein the precursor material comprises one or more materials selected from the following: polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), and perfluoroorganosiloxane.

12. An electrochemical battery comprising: Conductive material layer; Multiple different precursor structures are arranged in a predetermined pattern on a first surface of the conductive material layer, wherein the different precursor structures cover a total surface area of ​​the first surface of the conductive material layer that is greater than or equal to 1% and less than or equal to 50%, and the different precursor structures have an average spacing of greater than or equal to 0.1µm and less than or equal to 50µm, wherein the non-conductive precursor material forming the precursor structures has a density of less than 10. -4 Ionic conductivity in S / cm; An electroactive material layer is disposed on the precursor material such that at least a portion of each different precursor structure is not blocked by the electroactive material layer. and A solid electrolyte interface layer is disposed on the exposed surface of the electroactive material layer and contacts each of the different precursor structures, wherein the different precursor structures are configured to form a surface structure that chemically connects the solid electrolyte interface layer and the conductive material layer.

13. The electrochemical cell of claim 12, wherein at least a portion of each different precursor structure extends through the electroactive material layer.

14. The electrochemical battery according to claim 12, wherein the solid electrolyte interface layer comprises one or more materials selected from: lithium carbonate (Li₂CO₃), lithium peroxide (Li₂O₂), lithium hydroxide (LiOH), lithium oxide (Li₂O), lithium fluoride (LiF), lithium nitride (Li₃N), polyolefin, hemicarbonate; and Each of the different precursor structures contains one or more materials selected from the following: polytetrafluoroethylene (PTFE), lithium fluoride (LiF), polyvinylidene fluoride (PVdF), and perfluoroorganosiloxane.

15. An electrochemical battery comprising: Conductive material layer; An electroactive material layer is disposed on the exposed surface of the conductive material layer; A solid electrolyte interface layer is disposed on the exposed surface of the electroactive material layer; and Multiple different surface structures, which can be freely obtained through the electroactive material layer and chemically bonded to the first surface of the conductive material layer and the solid electrolyte interface layer, wherein the non-conductive precursor material forming the surface structure has a density of less than 10. -4 Ionic conductivity in S / cm.

16. The electrochemical battery of claim 15, wherein the plurality of different surface structures comprise lithium fluoride (LiF), and The solid electrolyte interface layer comprises one or more materials selected from the following: lithium carbonate (Li2CO3), lithium peroxide (Li2O2), lithium hydroxide (LiOH), lithium oxide (Li2O), lithium fluoride (LiF), lithium nitride (Li3N), polyolefin, and hemicarbonate.

17. The electrochemical cell of claim 15, wherein the total surface area of ​​the first surface covering the conductive material layer with the different surface structures is greater than or equal to 1% and less than or equal to 50%, and The different surface structures have an average spacing of 0.1 µm or less than 50 µm.

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