Solid state polymer separator for lithium ion batteries

Abstract

A safe, thin, and highly conductive solid polymer separator for lithium-ion batteries is disclosed. This separator can be configured in solvent-free batteries and allows lithium ions to pass through channels via a polymeric structure. The lithium-conducting polymer can be formed by free radical polymerization and can include a lithium-conducting polymer having a polymeric carbonate solvent between iterative spacers, a lithium-conducting material, and reinforcing additives. Optionally, an interface coating can reside on one or more sides of the separator to ensure long-term operation. By utilizing such a separator in solid-state lithium batteries, battery cell assembly can be simplified, shrinkage can be reduced, and safety can be improved. Various methods for manufacturing solid polymer separators for lithium-ion batteries are disclosed.

Description

Background Technology

[0001] publicly available technical fields

[0002] This disclosure relates to chemistry, specifically to current generating devices. More specifically, this disclosure relates to the manufacture of battery components with certain improvements in separator manufacturing to improve the overall battery performance, safety, and conductivity.

[0003] Description of related technologies

[0004] Lithium-ion batteries, or Li-ion batteries, are rechargeable batteries commonly used in portable electronics and electric vehicles. Compared to previous battery technologies, lithium-ion batteries offer faster charging, greater capacity, and higher power density, resulting in higher performance in smaller, lighter packages. While there are many reasons why lithium has become an advantageous element in battery technology, the most important reason relates to its elemental structure. Lithium is highly reactive because it readily loses electrons from its outermost layer, making it easy for current to flow through the battery. As the lightest metal, lithium is much lighter than other metals commonly used in batteries, such as lead. This property is important for small objects like telephones, but also for cars that require many batteries. Finally, lithium ions and electrons readily move back to the positive electrode (cathode), allowing for multiple charge cycles. Innovations in lithium-ion battery technology have helped minimize the form factor of electronic devices while increasing their capacity. Without the advancements in lithium-ion batteries witnessed in recent decades, smartphones, smartwatches, wearable devices, and other modern electronic luxuries would simply not be possible.

[0005] Traditional lithium-ion batteries use a liquid electrolyte. The liquid electrolyte solution in a liquid electrolyte lithium-ion battery is used to regulate the flow of current during charging and discharging. Current “flows” through the liquid electrolyte solution between the anode and cathode, allowing the battery user to store and then use the stored electrical energy. More specifically, lithium ions move from the negative electrode (anode) to the positive electrode (cathode) through the electrolyte during discharge and return during charging. These lithium-ion batteries typically use an embedded lithium compound as the material at the cathode and graphite at the anode. Graphite in its fully lithilated state (LiC6) has a maximum capacity of 372 mAh / g.

[0006] While liquid lithium-ion batteries boast high energy density, no memory effect, and low self-discharge, they can pose safety hazards due to their flammable electrolyte content. If damaged and exposed to air or improperly charged, these batteries can cause or even lead to explosions and fires. Recalls of removable lithium-ion batteries due to fire hazards are common and costly, and some portable electronics manufacturers have been forced to recall expensive electronic devices without removable batteries due to lithium-ion fires. This issue is increasingly concerning due to the use of liquid lithium-ion batteries in electric vehicles (EVs). During and after an accident, the liquid lithium-ion batteries in EVs are highly flammable when exposed to water in the air, posing a significant safety concern. This safety issue becomes increasingly important as EVs become more commercially viable and widely adopted.

[0007] Much of the research and development efforts aimed at solving these problems in liquid lithium-ion batteries have focused on developing batteries with no liquid components. Solid-state lithium has a maximum potential capacity of 3600 mAh / g, nearly ten times that of LiC6. However, lithium metal is highly reactive even in its solid state, and its precipitates (plates) are highly non-uniform. Even in liquid electrolyte lithium-ion batteries, if the deposition rate exceeds the generally accepted low critical current (0.5 mA / cm²), the battery will be significantly affected. 2 Lithium can form dendritic or moss-like structures instead of smooth or flat deposits. This is why liquid lithium-ion batteries experience repeated electrolyte decomposition, bulging, swelling, and even breakdown. In conventional solid-state lithium foil anode batteries, this current rate is even lower (0.1 mA / cm²). 2 Therefore, just as many advancements in liquid electrolyte lithium-ion batteries have reduced the likelihood of dendritic or moss-like formations, developments to prevent this from occurring are even more crucial if solid-state lithium-ion anodes are to be produced. Batteries with larger energy storage capacities will be advantageous if charge and discharge rates fall within the range expected by consumers and manufacturers for modern liquid lithium-ion batteries.

[0008] Some research and development in solid-state lithium battery technology has focused on developing separators suitable for promoting solid-state lithium-ion batteries without liquid electrolytes. Separators are typically insulators that provide electron separation between the anode and cathode of the battery to prevent internal short circuits between each solid component. The fabrication of solid anodes and cathodes requires battery separators with structures, chemistry, and compositions sufficient to allow the incorporation of those other solid components (e.g., anodes and cathodes). Some separators previously developed for liquid lithium-ion batteries include polymer sheets, typically made of polyethylene and / or polypropylene (PE / PP). These sheets offer varying porosities (e.g., 35%–60%). These polymer sheet separators use a filled electrolyte, typically containing a lithium salt (e.g., LiPF6) dissolved in an organic solvent (e.g., ethyl methyl carbonate or dimethyl carbonate). They are of uniform thickness and can be as thin as 15 μm. The developed porous polymer sheet separators are generally still “perfect” insulators, despite the pores, meaning they do not conduct lithium ions or electrons, nor do they allow lithium ions or electrons to pass through the separator. Conversely, lithium ions pass through a liquid electrolyte filling the pores of the porous polymer sheet separator. At room temperature, the volumetric conductivity of liquid electrolytes in organic solvents is approximately 10 mS / cm. However, when they fill the insulating porous polymer sheet separator, the total lithium conductivity across the separator decreases by 100x, approaching 0.1 mS / cm at room temperature. Furthermore, porous polymer sheet separators exhibit area shrinkage at temperatures as low as 100°C, posing a risk of internal short circuits and thermal runaway if the anode is in contact with the cathode during use. Moreover, the use of PE / PP separators typically requires organic solvents in liquid form, meaning they may be unsuitable if a solid form factor is desired, due to the aforementioned reasons.

[0009] Therefore, it is evident that there is a recognized unmet need for improvements to battery separators to allow for truly solid separators for solid-state batteries, which permit a wide range of lithium-ion migration pathways. This disclosure aims to address this need through various improvements to components and internal structures, including the anode disclosed herein, while resolving at least some aspects of the problems discussed above. Summary of the Invention

[0010] In summary, in a possible preferred embodiment, this disclosure overcomes the aforementioned drawbacks and meets recognized requirements for such separators by introducing various improvements to the manufacture, construction, and design of the battery to accommodate a solid separator within a solid-state lithium-ion battery. These typically include, but are not limited to, the individual or combined incorporation of novel and / or suitable lithium-conducting polymers, solid polymer electrolyte (SPE) composites, and interfacial coatings. By allowing the use of solid-state lithium-ion separators, these improvements have the potential to increase the energy storage capacity of lithium-ion batteries from the theoretical maximum in the form of liquid electrolytes to the higher energy density of solid forms without sacrificing conductivity across the solid separator. Furthermore, these individual and / or combined improvements help reduce potential hazards, such as fires, caused by lithium-ion battery swelling, bulging, or damage. These individual and / or combined improvements can achieve these advantages without sacrificing reduced charging speed, decreased conductivity, increased volume or weight, and reduced power supply to the device.

[0011] One aspect of solid separators for solid-state lithium-ion batteries is the incorporation of novel lithium-conducting polymers. Lithium-conducting polymers can be manufactured in various forms, each with its own advantages and trade-offs. These variations in form can be better understood as individual, different implementations of the lithium-conducting polymer, or as combinations thereof, to achieve a balance of advantages and trade-offs.

[0012] In a possible preferred embodiment, the lithium-conducting polymer may comprise polymerized carbonate blocks (i.e., polymers derived from the polymerization of carbonate solvents) rather than polyethylene glycol-based blocks (ethylene oxide or PEO). Carbonate solvents have higher polarity and provide higher conductivity for lithium ions. Carbonate solvents also have improved oxidative stability due to the delocalization of free electrons on carbonyl groups. Therefore, for the construction of solid-state lithium-ion membranes, polymer blocks derived from carbonate solvents such as vinylene carbonate, ethylene carbonate, or propylene carbonate may be superior to PEO. Furthermore, carbonates may additionally have a conductivity advantage over PEO. Due to the increased conductivity, many advantages can be obtained when using, manufacturing, and implementing high-voltage cathodes (e.g., nickel manganese cobalt cathodes, nickel cobalt aluminum oxide cathodes, and / or lithium cobalt oxide cathodes). Ether-based solvents and polymers derived therefrom (such as PEO) are generally incompatible with high-voltage cathodes and can only be used with low-voltage cathodes (e.g., lithium iron phosphate cathodes). Carbonate-derived polymers promote electron delocalization and exhibit higher oxidative stability, enabling these higher-voltage cathode technologies to be configured in conjunction with suitable membrane technologies. An exemplary method of polymerizing such carbonate solvents is by polymerizing olefin bonds in the solvent via free radical polymerization. Various improvements to the use of these carbonate solvents in polymerizable form will become more apparent to those skilled in the art when reading the following brief description of the accompanying drawings, detailed description of exemplary embodiments, and claims, with reference to the accompanying drawings or figures. These improvements include increased solubility, consideration of chemical structure, increased lithium conductivity, and the addition of spacers and cyclic monomers.

[0013] Another option for solid separators used in solid-state lithium-ion batteries is a solid polymer electrolyte (SPE) composite material. Solid polymer-based separators can contain lithium-conducting materials with electronic insulating properties. Materials with low material density may be required to produce battery cells with high energy density. Typically, the lowest density solid materials manufactured today are polymers with chemical structures (microstructures), which contribute to low-density macrostructures. Therefore, polymers capable of conducting lithium can be suitable materials for the structure of such separators used to form solid-state battery cells with high energy density. Lithium conductivity in the polymer can be promoted or made possible by Li+ coordination or conductive sites within the structure with high mobility. Such groups can include ethereal oxygen, carbonate oxygen, or silicon-based polymers with similar functionality, such as siloxanes. Other Li+ conductive sites on the polymer can be nitrogen, phosphorus, or sulfur-based, as found in polydopamine, polyimide, polyphosphazene, or polysulfonates. Separators with a thickness of less than 20 micrometers are preferred because they allow for both independent structure and stability in humid air. The fabrication of this structure could also facilitate its adoption within the existing battery industry. An existing problem hindering the adoption of this separator material in the battery industry is that polymers with high lithium conductivity typically have short chains, which may prevent them from forming thin, discrete films. The strength modulus of these lithium-conducting polymers can be improved by forming composite materials through mixing with inorganic materials. These inorganic materials can be expected to possess lithium conductivity and low density properties. Such inorganic additives could be lithium aluminum titanium phosphate (LATP, Li... 1.5 Al 0.5 Ti 1.5 (PO4)3), Lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O) 12 ), LSPSCl(Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 ), LGPS (Li 10 GeP2S 12 Alternatively, lithium-conducting halides and closed / nested borates may be used. Electronically insulating carbon-based additives and clays may also be used. Finally, inorganic additives, which are retained as a small fraction of the composite material, such as less than 10% of the total membrane by weight, volume, and / or mass, can be significant.

[0014] In some of the various possible preferred embodiments in this regard, various manufacturing techniques and standards can be important for the manufacture of both the solid separator and the solid-state lithium-ion battery. These may include electrospinning of the conductive polymer and SPE and / or blade casting of the conductive polymer and SPE. Those skilled in the art will understand that certain polymers, certain SPEs, and certain combinations thereof may require one, another, or a combination of these techniques. Various modifications including SPEs and conductive polymers will become more apparent to those skilled in the art when reading the following brief description of the accompanying drawings, detailed description of exemplary embodiments thereof, and claims with reference to the drawings or figures.

[0015] In another aspect of solid separators for solid-state lithium-ion batteries, the separator may include one or more interface coatings, as lithium conductivity can be maximized on thin (<20 micrometers) solid separators. At this thickness, the interface with the anode or cathode may require additional treatment to ensure long-term operation. This can be a serious problem for stability, durability, and safety, especially at the interface with the exposed lithium metal anode. Several coatings can stabilize and promote this interface. These include carbon materials and macromolecules such as graphite and graphene, nitrides, borates, alloys, sulfur-based coatings, fluoroethylene carbonate with cathode stabilizer additives, and / or combinations thereof. Various improvements to the interface coatings will become more apparent to those skilled in the art when reading the following brief description of the figures, detailed description of exemplary embodiments thereof, and claims with reference to the accompanying drawings and figures.

[0016] Individually or in combination with features generally associated with solid-state lithium-ion batteries, solid separators for solid-state lithium-ion batteries outperform conventional liquid electrolyte lithium-ion batteries in all aspects and characteristics, as well as existing, available, experimental, and / or proposed solid-state lithium-ion batteries and their respective separators. One advantage of solid separators for solid-state lithium-ion batteries is their ability to increase the battery's energy density to levels higher than those of currently commercially available batteries with liquid battery cells. Another advantage of solid separators for solid-state lithium-ion batteries is their ability to achieve energy densities higher than the currently observed 0.1-0.5 mA / cm² for solid-state batteries. 2 It operates at high current, approaching 10 mA / cm². 2This can have significant commercial implications for charging high-energy-density batteries in less than 30 minutes. Another feature of solid-state lithium-ion batteries is that they enable safe lithium metal battery structures with a lithium-philic interface, which can lead to high cycle life (e.g., greater than 4000 cycles), which can also have commercial implications for electric vehicles and other durable goods requiring long-lasting battery installations. Another feature of solid-state lithium-ion batteries is their ability to operate over a wider temperature range (e.g., -60°C to 150°C) than currently available commercial liquid-based batteries (-30°C to 60°C). Another feature of solid-state lithium-ion batteries is their ability to achieve pre-lithiated anodes during manufacturing. Another feature of solid-state lithium-ion batteries is their ability to fabricate bipolar battery cells. Bipolar battery cells utilize bipolar current collectors, with an anode on one side and a cathode on the other. This would otherwise be impossible, and it is unknown whether liquid-containing separators are possible, as the liquid flows between the stacks and creates ion short circuits and electrolyte decomposition. Solid separators that do not contain liquid enable bipolar battery cells, a factor contributing to higher charging rates due to the lower internal resistance of bipolar cells. Bipolar cells may also be safer for various reasons, including because they operate with less cell Joule heat. In some embodiments, another feature of the solid separator for solid-state lithium-ion batteries may be a polymer / inorganic composite material that may contain flame retardants that are non-flammable and safer than liquid-containing separators. Another feature of the solid separator for solid-state lithium-ion batteries may be enabling other battery components to be solid lithium-ion (e.g., solid anode, solid cathode). Finally, various other features of the solid separator for solid-state lithium-ion batteries can include additional potential advantages, such as, but not limited to, low-density and lightweight materials, high energy density, sheet fabrication capability with large surface areas, ability to be manufactured in untreated atmospheric air, high electrochemical stability, high ratio solvation of lithium per unit weight or molar ratio, high stability of lithium at the anode / cathode interface, high strength, and / or combinations thereof.

[0017] These and other features of the solid separator for solid-state lithium-ion batteries will become more apparent to those skilled in the art when reading the preceding overview and the following brief description of the accompanying drawings, detailed description of exemplary embodiments thereof, and claims, with reference to the accompanying drawings or figures. Attached Figure Description

[0018] A better understanding of the solid separator used in solid-state lithium-ion batteries will be achieved by referring to the accompanying drawings. The drawings are not necessarily drawn to scale, and the same reference numerals indicate similar structures and refer to the same components throughout.

[0019] Figure 1This is a cross-sectional perspective view of an exemplary embodiment of a high-energy-density lithium metal-based battery for solid-state lithium-ion batteries disclosed herein.

[0020] Figure 2 This is a diagram of the components of a battery in the current field.

[0021] Figure 3 This is a cross-sectional perspective view of an exemplary embodiment of a solid separator for solid-state lithium-ion batteries.

[0022] Figure 4 This is a block diagram of a battery.

[0023] It should be noted that unless the drawings presented are deemed essential to the claimed disclosure, they are for illustrative purposes only, and therefore are neither intended nor intended to limit this disclosure to any or all the exact details showing the construction. Detailed Implementation

[0024] In describing exemplary embodiments of this solid separator for solid-state lithium-ion batteries, as Figure 1 -5. For clarity, specific technical terms are used in the illustrations. However, this disclosure is not intended to be limited to the specific technical terms chosen, and it should be understood that each particular element includes all technical equivalents that operate in a similar manner to achieve similar functions. However, embodiments of the claims can be implemented in many different forms and should not be construed as limited to the embodiments set forth herein. The examples set forth herein are non-limiting examples and are merely examples among other possible examples. It should be noted that the terms battery, cell, anode, cathode, and separator are used in both singular and plural forms because they relate to the high energy density lithium metal-based anode of the solid-state lithium-ion battery used in this disclosure, as well as to describe other batteries, including but not limited to lithium-ion batteries with a liquid electrolyte. Although a single cell of a battery is described herein, those skilled in the art of battery manufacturing will understand that multiple cell units can be used in the design, construction, manufacture, and assembly of batteries, and that multiple cells can be arranged and / or installed within a finished manufactured product. While fiber frames and one or more fiber sheets are used throughout the detailed description, they can also be understood as fibrous battery skeletons and separator microstructures, respectively.

[0025] Now for reference Figure 1-5, for example and not as a limitation, wherein, in addition to the high energy density lithium solid anode 111 for solid-state battery 100, an exemplary embodiment of a solid separator 131 for solid-state lithium-ion battery is also illustrated. Solid-state battery 100, liquid electrolyte battery 200, and battery 300 may be referred to herein simply as batteries. Solid separator 131 and porous separator 231 for solid-state lithium-ion battery may be referred to herein simply as separators. High energy density lithium metal-based solid anode 111, liquid electrolyte anode 211, and anode 311 may be referred to herein simply as anodes. Although variations in construction, design, composition, chemistry, and assembly may relate to cathode 312, for clarity and consistency, in Figure 1 In section -5, any reference to cathode 312 is only for the cathode, and other relevant features may be mentioned in the description as it relates to solid-state battery 100, liquid electrolyte battery 200, and battery 300. Solid-state battery 100, liquid electrolyte battery 200, and battery 300 can be charged via charger 351 and can be discharged to power receiving device 352. As described herein, solid-state battery 100, liquid electrolyte battery 200, and battery 300 may each have a single battery cell or may have multiple battery cells connected and / or assembled in a multilayer of anode 311, cathode 312, and separator 331. Lithium, lithium metal, elemental lithium, and lithium ion are used interchangeably herein, and this disclosure is not limited to batteries having lithium metal as their current element. Other elements may include, but are not limited to, zinc, sodium, cobalt, nickel, lead, potassium, other metals, their salts, and / or combinations thereof. In a potentially preferred exemplary embodiment, the solid-state battery 100 may include the following components: a solid anode 111 having a solid electrolyte 112 with a fiber frame and showing a metal ion deposit 120, a solid separator 131, and a cathode 312 having a solid cathode current collector 132. In an embodiment of the liquid electrolyte battery 200, the liquid electrolyte battery 200 may include the following components: a liquid electrolyte anode 211 having a graphite anode active material 212 and an anode current collector 233, a porous separator 231, and a cathode 312 having a liquid electrolyte cathode current collector 232. In an embodiment of the battery 300, the battery 300 may include the following components and connectors: an anode 311, a cathode 312, a separator 331, a charger 351, and a power receiving device 352.

[0026] Now for more specific reference Figure 1 The example shown is of a solid-state battery 100. Starting from the top is a solid anode 111, with solid separators 131 above and below the solid anode 111. The solid anode 111 can be formed of one or more layers of solid electrolyte 112, where each layer of solid electrolyte 112 can be formed of a fiber framework. Typically, the solid anode 111 can be understood as releasing electrons to an external circuit (see [reference]). Figure 4The cathode 312 is the negative or reducing electrode that is oxidized during the electrochemical reaction. It can be understood as acquiring electrons from an external circuit (see...). Figure 4 The positive electrode or oxide electrode is reduced during the electrochemical reaction. In this possible preferred embodiment, the solid anode 111 may include a solid electrolyte 112, which can be understood as a framework of interconnected fibers. The interconnected fibers in the framework of the solid anode 111 can have a variety of properties and can be flexible or rigid. In the case of a ceramic fiber framework, ceramic can be used to provide structure, support, and a surface where lithium or other metals can be deposited for the solid anode 111 and the solid-state battery 100. The lithium metal at the metal ion deposit 120 can provide electronic conductivity for the solid-state battery 100, while the solid ceramic framework / skeleton can provide volumetric support, a surface layer for the metal ion deposit 120, and lithium-ion conductivity. During charging and discharging of the solid-state battery 100, the size of the metal ion deposit 120 can grow toward the solid separator 131 or shrink toward the center of the solid anode 111. A method of combining, manufacturing, and / or operably joining the metal ion deposit 120 with the fiber framework of the solid electrolyte 112 can be achieved by injecting molten lithium metal into the treated ceramic framework. Initially, only a small amount of lithium metal may need to be injected into the pre-cell assembly of the solid anode 111. In this case, only a small amount is injected into the pre-cell assembly of the solid anode 111, while most or even all of the reversible lithium that gives the cell capacity can come from the cathode 312 in the final assembly. Therefore, during the first charge of the solid-state battery 100 and during all subsequent charges, the metal ion deposit 120 can be detected or observed to be very small at or near the center of the solid anode 111. During the charging process of the solid-state battery 100, the metal ion deposit 120 can be detected or observed to grow outward toward the solid separator 131, and even along the solid electrolyte 112 to occupy all the space within the fibrous frame of the solid anode 111. Deposition of lithium and / or other metals may additionally occur by temporarily inserting high voltage into cathodes such as lithium iron phosphate (LFP), lithium cobalt oxide (LCO), nickel / manganese / cobalt (NMC), etc., and / or combinations of various cathodes thereof. The higher surface area of ​​the solid electrolyte 112 with a ceramic fiber framework compared to a flat lithium foil allows for a higher operating rate (lithium deposition / dissolution) of the solid-state battery 100. However, a flat lithium foil can also be used as the initial form of the metal ion deposit 120 and can also be melt-injected along the center of the solid anode 111 in the solid electrolyte 112.

[0027] From an energy density perspective, a key requirement for the ceramic fiber framework of solid electrolyte 112 is the use of low-density ceramics. A suggested example of a low-density, lightweight ceramic is Li. 1+x Al x Ti2-x P3O 12 (LATP). In this embodiment of a solid anode 111 having a solid electrolyte 112 including ceramics, there may be additional components, manufacturing methods, and other variations, including various advantages and trade-offs. These may include the selection of processing types for active and functional materials. In a potentially preferred embodiment of the ceramic class of solid electrolyte 112, a coating material having specific metallic qualities that attracts particular metallic properties may provide further advantages to facilitate smooth, consistent precipitation along the internal fibrous framework. These may include an engineered solid anode 111 having solid electrolyte 112 to measure a total thickness of approximately 80-90 μm per layer, a total length and width of approximately 5 cm x 5 cm along the solid membrane 131, a porosity of more than 70% of the internal fibrous framework, a single and / or average fiber diameter of less than 0.35 μm, a single and / or average fiber length of more than 1 mm, a coating thickness of approximately 10 nm, and a coating material including oxides, nitrides, polymers, or ceramics. The oxide coating material for the fibers in the solid electrolyte 112, for example but not limited to, includes, but is not limited to, niobium, Al₂O₃+ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur oxides and / or combinations thereof. The nitride coating material for the fibers in the solid electrolyte 112, for example but not limited to, boron, vanadium nitride, and combinations thereof. The polymer coating material for the fibers in the solid electrolyte 112, for example but not limited to, succinonitrile (SCN). The ceramic coating material for the fibers in the solid electrolyte 112, for example but not limited to, closed borate (CB), lithium phosphorus oxynitride (LiPON), and / or combinations thereof. By using one or more coatings on the ceramic fiber structure of the solid electrolyte 112, ceramics that may not readily bond with lithium or other metals can be promoted to bond with lithium, thereby acting as an electrolyte, on which solid metals, including lithium ions, can move freely during charging and discharging.

[0028] In a second potentially preferred embodiment regarding the lithium conductor of the solid anode 111 for the solid-state battery 100, a polymer framework in the solid electrolyte 112 is preferred. The polymer framework of the solid electrolyte 112 within the solid anode 111 can provide the additional advantage of flexibility, where the previous ceramic fiber framework of the solid electrolyte 112 in the solid anode 111 can be described as rigid. This can provide various advantages and trade-offs at both the level of a single cell or a layer of the solid-state battery 100, but also various trade-offs and advantages for the power receiving device 352 on which the solid-state battery 100 is mounted. The requirements for the polymer framework of the solid anode 111 and the materials deposited therein can be (a) a melting point higher than the melting point of lithium metal (180°C), (b) non-conductive properties of lithium ions, and (c) the injection of lithium-conducting materials into the structure of the solid electrolyte 112, such as other conductive polymers having a corresponding lithium salt (e.g., lithium bis(trifluoromethanesulfonyl)imide / LiC2F6NO4S2 / LiTFSI) or ceramic particles embedded in the polymer and / or on its surface. In this embodiment of the solid anode 111 with a polymer framework of solid electrolyte 112, there may be additional components, manufacturing methods, and other variations, including various advantages and trade-offs. These may include a fiber mat extending throughout the solid anode 111 and solid electrolyte 112, which may further include aramid and polyimide frameworks. Furthermore, while not all coatings used for ceramic fiber frameworks are suitable for polymer or polymer fiber frameworks, and while not all properties and characteristics of ceramic fiber frameworks are directly applicable to polymer or polymer fiber frameworks, some are. These may include an engineered solid anode 111 with solid electrolyte 112 measuring a total thickness of approximately 80-90 μm per layer, a total length and width of approximately 5 cm x 5 cm along the solid diaphragm 131, a porosity of more than 70% of the internal fiber framework, a single and / or average fiber diameter of less than 0.35 μm, a single and / or average fiber length of more than 1 mm, a coating thickness of approximately 10 nm, and a coating material including oxides, nitrides, polymers, or ceramics. The oxide coating material for the fibers in the solid electrolyte 112, for example but not limited to, includes, but is not limited to, niobium, Al₂O₃+ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur oxides and / or combinations thereof. The nitride coating material for the fibers in the solid electrolyte 112, for example but not limited to, boron, vanadium nitride, and combinations thereof. The polymer coating material for the fibers in the solid electrolyte 112, for example but not limited to, succinonitrile (SCN). The ceramic coating material for the fibers in the solid electrolyte 112, for example but not limited to, closed borate (CB), lithium phosphorus oxynitride (LiPON), and / or combinations thereof.By using one or more coatings on the ceramic fiber structure of the solid electrolyte 112, it is possible to promote the bonding of the ceramic, which is not easily bonded to lithium or other metals, with lithium, thereby acting as an electrolyte, on which solid metals including lithium ions can move freely during charging and discharging.

[0029] In a potentially preferred embodiment, including a ceramic or polymer fiber framework for the solid anode 111 and solid electrolyte 112, the initial lithium deposits may be important for several reasons. These may initially form at the metal ion deposit 120 in very small, almost negligible amounts, but their size, weight, and volume increase, and they may even occupy all the empty space within the solid anode 111 and solid electrolyte 112. This can be achieved by various methods, although a potentially preferred process for initial metal deposition near the center of the solid anode 111 on the surface of the solid electrolyte 112 and its fibers is melt injection via lithium foil.

[0030] Furthermore, the fabrication of the fibers themselves, whether ceramic or polymeric, can provide a variety of important improvements to the structure, formation, and overall properties of the solid electrolyte 112, solid anode 111, and solid-state battery 100. These technologies may have few known applications in the battery technology industry, but could have significant applications in materials science and nonwovens. One such process could include a sol-gel process, which can preferably occur prior to the deposition of the metal ion deposit 120. In this chemical process, a “sol” (colloidal solution) can be formed, which then gradually evolves into a gel-like two-phase system containing both liquid and solid phases, with morphologies ranging from discrete particles to continuous polymer networks. In the case of colloids, the volume fraction of particles can be so low that a significant amount of fluid may initially need to be removed to identify the gel-like properties. One such fluid removal method could be simply allowing time for sedimentation to occur and then pouring out the remaining liquid. Centrifugation can also be used to accelerate the phase separation process. Removing the remaining liquid (solvent) phase requires a drying process and can result in substantial shrinkage and densification. The rate of solvent removal is ultimately determined by the porosity distribution within the gel. The final microstructure of the final component is strongly influenced by changes applied to the structural template during this processing stage. Heat treatment or sintering processes are often necessary to promote further polycondensation and enhance mechanical properties and structural stability via final sintering, densification, and grain growth. One significant advantage of this approach compared to more conventional processing techniques is that densification is typically achieved at much lower temperatures. Precursor sols can be deposited on substrates to form films (e.g., by dip coating, spin coating, or electrospinning), cast into suitable containers with desired shapes (e.g., to obtain monolithic ceramics, glass, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres). This technique, combined with electrospinning, is known to produce paper-like materials with open cavities, which may be well-suited for depositing metals, i.e., lithium ions. Further processes that enhance this space-filling and open-cavity characteristic of the solid electrolyte 112 can include co-precipitation, evaporation, self-assembly, and the utilization of nanoparticles, using various compositions of the disclosed ceramics and polymers.

[0031] In ceramic or polymeric embodiments of the solid electrolyte 112, materials with open cavities in their fibrous structure, or materials with a lithiophilic coating in their fibrous structure, can be considered active materials, including the solid anode 111. In other words, the active material of the solid anode 111 can be the solid electrolyte 112, which is the active material through which lithium ions migrate and accumulate at the metal ion deposit 120. Any active material manufactured to create the solid anode 111 can be processed into a functional material having these properties and serving as the solid electrolyte 112 of the solid-state battery 100. The first stage of this process can be the synthesis of a fibrous felt comprising substances such as LATP, closed borates, and sulfide ceramics. The sol-gel stage or other processes forming the open-cavity structure of the solid electrolyte 112 can be improved by reducing the firing temperature required to implement heterovalent substitution. Other improvements may include maximizing density through the use of flux additives (e.g., Li₂O, MgO, ZnO, Li₃PO₄, Li₃BO₃, B₂O₃, LiBO₂, Al₂O₃, Ta, Nb, Y, Al, Si, Mg, Ca, YSZ, NiO, Fe₂O₃, etc. and / or combinations thereof). To achieve functional material processing for the solid electrolyte 112, it may be necessary to pre-assemble the active material of the solid electrolyte 112 to obtain a robust functional laminate, sheet, or felt for use as a solid anode 111. Slurry additives may be added to process the green laminate during a rapid sintering process. These slurry additives may include, but are not limited to, resins, oils, and dispersants (e.g., PAA, glucose, PVP, ethylene glycol, oleic acid, ultrasonic horn, etc. and / or combinations thereof). Sintering the green material using conventional techniques known to those skilled in the art can be a lengthy process (>10 hours) and may require high temperatures (>1250°C). These traditional requirements can lead to high operating costs, are difficult to scale up, and result in undesirable lithium loss due to evaporation during sintering. Lithium loss at these times and temperatures may need to be offset by using additional lithium salts during synthesis, which only further increases costs. An alternative approach should be to allow scalable application in an open atmosphere and prevent lithium loss or consumption. The resulting sintered green laminate should contain voids for lithium metal melt infusion, which may occur at room temperature after sintering. As mentioned above, these voids can be constructed by using sacrificial plastic / carbon beads or by electrospinning them into a fibrous felt. The resulting solid electrolyte 112 can then be used to deposit lithium along the metal ion deposit 120.

[0032] Alternative measures to enhance these properties in the solid electrolyte 112, thereby creating an optimal solid anode 111, may include, but are not limited to, reactive sintering of the starting material, sintering in an electric field, microwave sintering, SPS or spark plasma, cold sintering using solvent evaporation and salt CSP, and rapid sintering using high current. Alternatively, or in combination with these techniques for developing the solid electrolyte 112, porous sheets can be fabricated using sacrificial beads, which are various plastics or carbons with low evaporation temperatures, which can be removed and / or destroyed, leaving openings in the fiber felt, or ceramic fiber felts can be developed via electrospinning. Other anticipated methods, particularly suitable for polymer fiber classes of solid electrolyte 112, include the use of polymers with a lithium metal melting point (180°C). However, these polymers are generally not lithium-ion conductive, therefore they will serve a structural role under which additional lithium-conducting materials, such as other conductive polymers (with corresponding lithium salts, such as LiTFSI) or ceramic particles, can be implanted into the structure. For example, fiber mats comprising polyimide (with a melting point of 450°C) can be used to inject molten lithium and serve as a coating. Other examples include aromatic polyamides and polyimide frames. Yet another example providing a suitable composition for the solid electrolyte 112 could be a hybrid composite structure possessing both polymer fiber and ceramic fiber properties. Hybrid composite fiber mats could comprise fumed silica and surface-doped boron / vanadium (or other nitrides) G4 / LiTFSA.

[0033] More important for the surface structure and composition of the solid electrolyte 112 may be coating alternatives, which can provide additional advantages, alone or in combination, for the deposition, mobility, and smooth precipitation of the metal ion deposit 120. These can include CVD / PVD / PECVD and / or ALD vapor deposition combined with AZO coatings, using I2, Li3N, Li3PO4, LLZO, Li9AlSiO8, Li3OCl, LiI:4CH3OH, or metals with good lithium alloying properties, including but not limited to aluminum, indium, zinc, magnesium, silicon, and / or gold. Solution coatings can also be used on the solid electrolyte 112, or to form key components of the solid electrolyte 112. These solution coatings can be developed using sulfur-based solution coating methods that utilize solutions such as polysulfides dissolved in DEGDME, sulfur-dissolved ZnO-doped silver sulfide germanium ore Li6PS5Br, Li2S3, or Li3S4. Polymer coatings can also be used as surface coatings for the solid electrolyte 112, and may include SN / FECs with additives and salts (e.g., CsPF6, CsTFSI, LiNO3, LiF, CuF2), elastomers such as SHP, and even binders such as polydopamine and / or polysiloxanes. These various coatings for the solid electrolyte 112 can provide a range of advantages, including reducing lithium dendritic growth at the metal ion deposit 120 and during deposition on the solid electrolyte 112, expanding the possible choices of solid electrolyte 112 compositions for various applications, and preventing reactions between various very useful materials used to construct the solid anode 111 and lithium or other metals.

[0034] Alternatively, this document envisions that the metal ion deposit 120 could be replaced by an anode current collector in a solid anode 111 disposed in a solid electrolyte 112. These could include a foil or coating on which a metal, particularly lithium, could be deposited. Exemplary materials for the anode current collector in the solid anode 111 disposed in the solid electrolyte 112 could include, but are not limited to, vanadium nitride, one or more lithium-aluminum alloys, liquid metals including gallium, indium, and tin, and / or combinations thereof.

[0035] Now for specific reference Figure 2 The diagram shows an example of a cross-sectional view of a battery cell of a liquid electrolyte battery 200. Typically, a conventional lithium-ion battery, as a liquid electrolyte battery 200, may include a liquid electrolyte anode 211 having a graphite anode active material 212 and an anode current collector 233, a porous separator 231, and a cathode 312 having a liquid electrolyte cathode current collector 232. Known variants of lithium-ion batteries with liquid electrolytes can achieve capacities of 275 Wh / kg and have rechargeability, but suffer from the serious drawbacks described in the background section above.

[0036] If sufficient open space is obtained while maintaining the structure, smooth lithium deposition, and other considerations described herein, the solid-state battery 100 can achieve substantially higher capacity, while allowing additional advantages such as durability, safety, fast charging, and others mentioned above. For example, a liquid electrolyte battery 200 with a capacity of 275 Wh / kg can be compared to the solid-state battery 100 of this disclosure, which has various forms and combinations and achieves capacities of 635 Wh / kg and above.

[0037] Various exemplary and suitable solid-state anodes for solid-state lithium-ion batteries have therefore been described, and now specific references are made to them. Figure 3 The illustration shows a cross-sectional perspective view of an exemplary embodiment of a solid separator 131 for a solid-state lithium-ion battery. Broadly speaking, the solid separator 131 for a solid-state lithium-ion battery can be formed as one or more sheets, each sheet having a microstructure characterized by the various modifications and features described herein. These may include, but are not limited to, a primary polymer 520 (illustrated as the thicker of two sets of long fibers running through the solid separator 131), a structural polymer 530 (illustrated as the thinner of two sets of long fibers distributed throughout the solid separator 131), and reinforcing additives 510 (illustrated as a set of circles distributed throughout the solid separator 131). It should be understood that while each side of the solid separator 131 may have unique or distinct characteristics, qualities, chemical composition, etc., and / or combinations thereof, the top surface 313 and the bottom surface 113 may be considered to have undefined characteristics for the purposes of this disclosure. That said, the top surface 313 should be operatively bonded to the cathode 312, and the bottom surface 113 will be operatively bonded to the anode 311 (or liquid electrolyte anode 211). This does not mean that the bottom surface 113 is operatively engaged with the cathode 312, or the top surface 313 is operatively engaged with the anode 311, but simply that the anode will be located opposite the cathode of the solid diaphragm 131. Although not drawn to scale, nor depicted to explicitly portray the microscopic appearance or structure of the solid diaphragm 131, Figure 3 Exemplary illustrations are provided to further illustrate the purpose, structure, and formation of the solid diaphragm 131. Furthermore, those skilled in the art will understand... Figure 3 The diagram illustrates the cross-sectional properties and helps to understand that it may represent a small fraction of the material required even for a single solid-state lithium-ion battery cell. The thickness of the solid separator 131 can be understood as generally uniform, but at the microscopic level, variations in thickness may be apparent. The solid separator 131 can be understood as very thin, with a high surface area and low density. Other objective qualities of the solid separator 131 are understood and described in this paper.

[0038] Now we turn to the basic structure and chemical composition of the solid membrane 131, such as Figure 3 The diagram illustrates the main polymer 520, the structural polymer 530, and the reinforcing additive 510.

[0039] Main polymer 520, such as Figure 3 The diagram shows that the solid separator 131 can be repeated along its length, width, and depth, and can be understood as being widely and / or uniformly distributed throughout the solid separator 131. As mentioned above, conventional lithium-conducting polymer electrolytes can be based on polyethylene oxide (PEO). This series of electrolytes requires temperatures above 45°C to provide conductivity above 0.1 mS / cm, typically around 60°C. A wider temperature range providing similar conductivity is necessary for appropriate industry adoption. PEO is a class of polymers of ether solvents known to conduct lithium ions. Ether solvents are not used in liquid battery cells because their low polarity results in low lithium-ion conductivity. In other words, PEO polymers inherit the disadvantages of their monomer composition. However, carbonate solvents have higher polarity than ether solvents and generally provide higher conductivity for lithium ions. Carbonate solvents also have improved oxidative stability due to the delocalization of free electrons on the carbonyl groups. Therefore, it is desirable to use polymers derived from carbonate solvent monomers in the main polymer 520 to enable the solid separator to conduct lithium ions while improving oxidative stability. Vinylene carbonate, ethylene carbonate, or propylene carbonate each provide suitable monomers for their respective polymers, as do combinations of these carbonates as monomers in sequence for the carbonate polymer. Furthermore, due to their ability to allow electron delocalization, the exemplary solid membrane 131, including polymers derived from carbonates, can provide the additional advantage of increasing the permissible voltage of the cathode 312, which might otherwise be impossible with a PEO-based membrane. Carbonates can be polymerized through a variety of chemical reactions, such as the exemplary chemical reaction of polymerizing olefin bonds in a solvent via free radical polymerization.

[0040] This document describes several exemplary polymers for the master polymer 520, each of which can be used alone or in combination in the solid separator 131. The concept of spacer monomers is important for each candidate polymer for the master polymer 520. Vinyl carbonate (VC) has the highest lithium-ion conductivity and is therefore an important candidate block material for the master polymer 520. However, due to its cyclic structure, it is highly rigid during polymerization, resulting in very low lithium conductivity in the resulting vinyl carbonate polymer. To increase its chain mobility and ultimately its lithium-ion conductivity, a series of "spacer" linear monomers can be inserted between the bulky VC cyclic monomers. Such "spacer" linear monomers can be glycol acrylates (e.g., butanediol and hexanediol) or ethylene glycol acrylates (e.g., triacrylate, diacrylate, and monoacrylate). Since the solubility of these combinations of molecules in solution can be challenging, the solubility of these materials can be improved by using ethylene oxides with high polarity epoxy in small molar ratios (e.g., glycidyl acrylate). Ethylene oxide can be polymerized with low-boiling-point amines in untreated atmospheric air after assembly to increase separator strength. Removing excess unpolymerized initiators or polymerization reactants such as azobisisobutyronitrile (AIBN) or amines can be important for maximizing cycle life and improving battery operation. Without removal, these highly reactive materials can accelerate battery degradation. Therefore, it is important to use polymerization mechanisms to strengthen separators with low-boiling-point reactants, allowing any excess to be easily evaporated during the drying step. In summary, this polymer candidate, in its basic trimer composition, can be understood as spacer + VC + ethylene oxide.

[0041] Other such polymer candidates for the main polymer 520 can be understood as having the following basic trimer compositions: spacer + prop-1-ene 1,3-sulfonolactone (PES) + ethylene oxide, spacer + 4-vinyl-1,3-dioxolane-2-one + ethylene oxide, spacer + allyl methyl carbonate + ethylene oxide, and polyacrylonitrile (PAN) + succinate (SCN). Specifically, succinate (SCN) can be an important additive for the main polymer 520 due to its properties as a highly conductive wax for lithium ions in the polymer state. SCN can be added to the solid separator 131 in various ratios to improve its conductivity as needed. For example, the low conductivity of PAN can be enhanced by a small ratio of SCN.

[0042] Structural polymer 530, such as Figure 3The diagram shows that the solid separator 131 can be repeated along its length, width, and depth, and can be understood as being widely and / or uniformly distributed throughout the solid separator 131. The most important or even crucial properties for the solid separator 131 are (i) lithium conductivity and (ii) electronic insulation. Additional properties that may be considered beneficial but not critical could be the low material density required to produce battery cells with high energy density. As mentioned above, the lowest density solid material is a polymer, making lithium-conducting polymers excellent candidates for the solid separator 131 to provide the framework for solid-state battery cells and impart high energy density properties. The lithium conductivity in the polymer is determined by Li+ coordination sites with high mobility. Such groups can include ether oxy, carbonate oxy, or silicon-based polymers with similar functionality, such as siloxanes. Other Li+ conductive sites on the polymer can be nitrogen, phosphorus, or sulfur-based, such as those found in polydopamine, polyimide, polyphosphazene, or polysulfonates. Preferably, the total thickness of the solid separator 131 should be less than 20 micrometers. The solid separator 131 should also be independent (self-sustaining) and stable in humid air. These requirements, in addition to benefiting the overall practicality and functionality of the solid separator 131, will encourage battery manufacturers in various markets to adopt the solid separator 131 and solid-state batteries in general. Polymers with high lithium conductivity typically have short chains, so they may not form thin, independent films on their own. Their strength modulus can be improved by mixing with inorganic materials such as reinforcing additives 510 to produce composite materials. It is desirable that, in addition to the main polymer 520 and the structural polymer 530, these inorganic materials that may include reinforcing additives 510 are also lithium-conductive and have low density. Such inorganic additives that may include reinforcing additives 510 can be LATP, LLZO, LSPSCl, LGPS, lithium-conductive halides, closed / nested borates, etc., and / or combinations thereof. Electronically insulating carbon-based additives may also be used to form reinforcing additives 510. Importantly, whether inorganic or carbon-based, reinforcing additives 510 are retained as a small component of the composite material while still being used for their reinforcing purposes. An exemplary amount of reinforcing additive 510 may be <10%.

[0043] The combination of the main polymer 520, structural polymer 530, and reinforcing additive 510, or any combination of two thereof, may be important to the overall usability, structure, function, and use of the solid diaphragm 131. An exemplary combination of the main polymer 520, structural polymer 530, and reinforcing additive 510 could be electrospinning. This can be understood as a method of combining polymers and inorganic materials into composites or forming polymer / inorganic composites. Furthermore, producing the solid diaphragm 131 by electrospinning and / or sintering the inorganic component into the polymer component can be understood as producing a highly porous mat (i.e., a fiber mat with >90% porosity), which can then be infused with a conductive polymer. Those skilled in the art of nonwoven materials manufacturing will understand that laboratory-scale electrospinning can typically be performed by applying high voltage between a metal syringe needle and a conductive plate. Electrospinning may be a more adaptable fiber spinning technique than conventional melt spinning. Electrospinning can be performed via a room-temperature process and can produce randomly arranged or well-arranged fiber mats, depending on the desired mat structure. The resulting fiber mat produced by this process can then be left exposed to ambient air while remaining non-reactive at room temperature. Hollow fibers can even be obtained using coaxial needles if a needle-based electrospinning method is employed. This method can further reduce the weight of the solid diaphragm 131. Unfortunately, there is currently no known method for scaling up this well-known laboratory procedure. However, following the same principle, viscoloids can be modified via a rotating conductive spiral to spin fibers under voltage without the use of needles. Using viscoloids, which are modified via a rotating conductive spiral to spin fibers under voltage without the use of needles, can be a scalable process. Exemplary materials that can be electrospun into fibers under these conditions include, but are not limited to, LATP, LLZO (inorganic), PI (polyimide-organic polymer), carbon (organic), aromatic polyamides (polymers), and / or combinations thereof. The use of modified viscous colloid technology using these exemplary materials may be important for the scalable production of electrospinning of the main polymer 520, structural polymer 530 and reinforcing additive 510 or any combination thereof, forming a solid diaphragm 131 as a solid porous felt.

[0044] The method of combining the main polymer 520, structural polymer 530, and reinforcing additive 510, or any combination of two thereof, may also include doctor blade casting to form a solid separator 131. By doctor blade casting a mixture of polymers, inorganic and / or lithium salts, those skilled in the art can form a robust, porous fibrous felt with the lightweight properties described herein, suitable for use as a solid separator 131. Doctor blade casting has another advantage as it has become a scalable process and is a known conventional process in the battery industry. For example, almost all battery electrodes can be assembled using this technique. This method of doctor blade casting of mixtures can provide further advantages in the solid separator 131, which includes polymer blends to achieve the desired strength at the desired thickness. However, if the main component of the solid separator 131 is a polymer composition, and if said polymer composition is also independent, obtaining a large-area solid separator 131 with a thin thickness (<20 micrometers) can be challenging. This method may be more suitable for a complete layered battery cell assembly process, in which the solid separator 131 is layered on top of the electrodes in a top-down, fully internal assembly of multiple battery cells. In this case, since the assembly can occur simultaneously with the fabrication of the solid separator 131, the aforementioned separate requirements are not necessary. Some materials, which can be used as components of the doctor blade casting slurry for manufacturing the solid separator 131, include, but are not limited to: fumed silica (inorganic additive) + G4 (tetraethylene glycol dimethyl ether, solvent) and / or LiTFSA (Li salt), LiBOB, LiTFSI, LiBF2(C2O4), LiBF2(C2O4), C2O4Li2, CF3CO2Li, C6H5COOLi, other lithium salts, and / or combinations thereof.

[0045] In addition to forming a solid separator 131 via electrospinning or doctor blade casting using a combination of the primary polymer 520, structural polymer 530, and reinforcing additive 510, or any two combinations thereof, it is more important to provide an interface coating (or bonding coating) at the interface with the anode 311 or cathode 312 to enable and / or improve the solid-state battery 100. Because maximizing lithium conductivity on a thin (<20 micrometers) solid separator 131 may be desired, additional treatment of the top surface 313 and / or bottom surface 113 of the solid separator 131 may be required to allow the anode 311 and cathode 312 to reside in such close proximity, even in the presence of the solid separator 131. In other words, the interface between the anode 311 and / or cathode 312 and the solid separator 131 may require additional treatment to ensure the long-term operation, durability, and sustainability of the solid-state battery 100. This can be a serious problem, especially at the interface with the exposed lithium metal of the solid anode 111. The interface coating can typically be applied, formed, or otherwise resided on the top surface 313 and / or the bottom surface 113. Exemplary coatings that can stabilize and promote the interface include, but are not limited to, graphite / graphene (i.e., carbon), nitride / borate (e.g., boron nitride, MgB2, Cu3N), metal alloys (e.g., Al coatings from AlX3 or Al(NO3)3 salts dissolved in solution, In coatings from In(TFSI)3, InF3, In(NO3)3, or salts dissolved therein), sulfur (e.g., Li2S+S, LPS), or FEC (i.e., fluoroethylene carbonate, a cathode stabilizer additive).

[0046] Now, let's get to the specifics. Figure 4 The diagram illustrates a simplified block diagram of a battery 300, which includes an anode 311, a cathode 312, a separator 331, a charger 351, and a power receiving device 352. When the cathode 312 makes conductive contact with the charger 351, it forms a circuit with the anode 311, thereby charging the battery 300. Alternatively, when the cathode 312 makes conductive contact with the power receiving device 352, it forms a circuit with the anode 311, and the power receiving device 352 is energized. Each of the charging and power supply occurs through any form of known electrochemical process between the anode 311 and the cathode 312. In addition to the various features, components, manufacturing methods, and improvements to the solid-state battery 100 as described herein, components and features of the battery 300 may be required for the complete manufacture and use of the solid-state battery 100. Furthermore, various improvements to the components of the battery 300, including those known and developed in the field of battery manufacturing, including the manufacture of the solid-state battery 100, can further enhance the advantages of the solid-state anode 111 as described herein. Simply replacing anode 311 with solid anode 111 may not be sufficient, and those skilled in the art of battery design and manufacturing can implement and apply the features of solid anode 111 to battery 300 in order to fully utilize the advantages disclosed herein.

[0047] Regarding the above description, it should be recognized that variations in optimal spatial relationships, including size, material, shape, form, location, function and operation, assembly, type of anode / cathode / cell container, type of one or more connections, and application, are all intended to be covered by this disclosure. It is contemplated herein that the high energy density lithium metal-based anode or solid anode 111, solid separator 131, and various parts and components described herein for a solid-state lithium-ion battery (solid-state battery 100) may include various overall dimensions and corresponding dimensions of various parts, including but not limited to: solid anode 111, solid electrolyte 112, metal ion deposit 120, solid separator 131, cathode 312, cathode current collector 132, etc., and / or combinations thereof. Indeed, during standard operation of the solid-state battery 100, the dimensions, shapes, etc., of those various parts and components of the solid-state battery 100 may vary. The high energy density lithium metal-based solid anode 111 for solid-state batteries 100, mentioned in conjunction with the description of the solid separator 131 herein, offers advantages for electric vehicles and other electronic devices. However, the invention is not limited thereto. The solid separator 131 for solid-state lithium-ion batteries of this disclosure, and the batteries manufactured therefrom, can be used to power applications such as other vehicles, computers, businesses, homes, industrial facilities, consumer and portable electronics, hospitals, factories, warehouses, government facilities, data centers, emergency backup, aerospace, spaceflight, robotics, drones, and / or combinations thereof. The chemical formulas, metals, atomic and molecular compositions (“Disclosed Formulas”) provided herein are merely exemplary. Those skilled in the art will recognize that variations of the disclosed Formulas can provide trade-offs for the solid separator 131 of this disclosure for solid-state lithium-ion batteries and can be substituted to achieve similar advantages as the solid separator 131 for solid-state lithium-ion batteries of this disclosure. Furthermore, various considerations regarding battery manufacturing may be considered due to variations in materials and manufacturing techniques, including but not limited to polymers, alloys, metals, assembly, joints, welding, atmospheric composition, and combinations thereof. However, although the inventors have considered various methods of manufacturing and assembling batteries to achieve one or more of the following results: greater energy density per unit mass, providing high operating current, increasing battery durability and lifespan, increasing the range in which the battery can operate reliably, providing safer batteries, and more efficient manufacturing methods, this disclosure is not limited to specific components, advantages listed and described herein, and / or manufacturing methods enumerated herein.

[0048] The foregoing description and accompanying drawings include illustrative embodiments. Exemplary embodiments have been described thus, and those skilled in the art should note that the disclosure herein is merely exemplary and various other alternatives, adaptations, and modifications can be made within the scope of this disclosure. Listing or numbering the steps of the method only in a particular order does not constitute any limitation on the order of the steps of the method. Many modifications and other embodiments will arise for those skilled in the art upon which this disclosure pertains, benefiting from the teachings presented in the foregoing description and associated drawings. Although specific terms may be applied herein, they are used only in a general and descriptive sense and not for limiting purposes. Therefore, this disclosure is not limited to the specific embodiments shown herein, but is limited only by the following claims.

Claims

1. A battery, the battery comprising: At least one cathode; At least one anode; as well as At least one solid membrane in contact with the at least one cathode and the at least one anode, the at least one solid membrane comprising a Li+ conductive main polymer, a structural polymer and a reinforcing additive, wherein the Li+ conductive main polymer, the structural polymer and the reinforcing additive are combined to form a Li+ conductive solid fiber mat; The Li+-conducting main polymer comprises a plurality of monomers, at least one spacer monomer, and at least one other monomer. The plurality of monomers are at least one monomer selected from the group consisting of vinylene carbonate, 4-vinyl-1,3-dioxolane-2-one, and allyl carbonate methyl ester, and the at least one other monomer is at least one monomer selected from the group consisting of ethylene oxide.

2. The battery according to claim 1, wherein, The at least one other monomer is glycidyl acrylate.

3. The battery according to claim 1, wherein, The Li+-conducting primary polymer further includes at least one of succinate and polyacrylonitrile.

4. The battery according to claim 1, wherein, The at least one solid membrane is independent and non-reactive at room temperature.

5. The battery according to claim 1, wherein, The structural polymer and the reinforcing additives are combined to form a solid polymer electrolyte composite material.

6. The battery according to claim 1, wherein, The reinforcing additive is lithium-conductive.

7. The battery according to claim 1, wherein, The Li+-conducting major polymer includes at least one lithium-ion coordination site from the group consisting of: ether oxygen, carbonate oxygen, silicon, nitrogen, phosphorus, and sulfur.

8. The battery according to claim 1, wherein, The Li+-conducting primary polymer further comprises at least one polymer from the group consisting of: polydopamine, polyimide, polyphosphazene, and polysulfonate.

9. The battery according to claim 1, wherein, The thickness of the solid diaphragm is less than 20 micrometers.

10. The battery of claim 1, further comprising an interface coating between the separator and the at least one cathode.

11. The battery of claim 1, further comprising an interface coating between the at least one solid separator and the at least one anode.

12. The battery according to claim 1, wherein, The battery is a lithium-ion solid-state battery, and the at least one anode and the at least one cathode do not contain a liquid electrolyte.

13. The battery according to claim 1, wherein, The reinforcing additive is present in an amount not exceeding 10% by weight.

14. The battery according to claim 1, wherein, The reinforcing additive is at least one additive from the group consisting of: LATP, LLZO, LSPSC1, LGPS, lithium-conducting halides, closed-type borates, and nested-type borates.

15. The battery according to claim 1, wherein, The structural polymer and the reinforcing additives are combined into a fiber mat via electrospinning.

16. The battery according to claim 1, wherein, The structural polymer and the reinforcing additives are bonded together to form a fiber mat via a doctor blade casting process.

17. A solid separator for a battery, comprising: The Li+ conducting main polymer comprises at least one monomer, at least one spacer monomer and at least one other monomer, wherein the at least one monomer is selected from the group consisting of vinylene carbonate, 4-vinyl-1,3-dioxolane-2-one and allyl carbonate methyl ester, and the at least one other monomer is selected from the group consisting of ethylene oxide. A structural polymer having at least one lithium coordination site; as well as Enhancement additives; The Li+ conductive main polymer, the structural polymer, and the reinforcing additive form a porous fiber felt, and a lithium conductive interface is coated on at least one side.

18. The solid diaphragm according to claim 17, wherein, The at least one other monomer is glycidyl acrylate.

19. The solid diaphragm according to claim 17, wherein, The Li+-conducting primary polymer further includes at least one of succinate and polyacrylonitrile.

20. A battery, comprising: At least one anode; At least one cathode; as well as A solid membrane in contact with at least one anode and at least one cathode, the solid membrane comprising a nonwoven fiber felt comprising a plurality of lithium-conducting polymers and a plurality of solid polymer electrolyte composites, the plurality of lithium-conducting polymers comprising a plurality of monomers selected from the group consisting of vinylene carbonate, 4-vinyl-1,3-dioxolane-2-one and allyl carbonate methyl ester, at least one spacer monomer, and at least one other monomer selected from the group consisting of ethylene oxide.

21. The battery according to claim 20, wherein, The at least one other monomer is glycidyl acrylate.

22. The battery according to claim 20, wherein, The plurality of lithium-conducting polymers further include at least one of succinic anhydride and polyacrylonitrile.

23. The battery according to claim 20, wherein, The nonwoven fiber felt is produced by electrospinning or doctor blade casting of the lithium conductive polymer and solid polymer electrolyte composite material.

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