Solid-state polymer separator for lithium-ion batteries

Abstract

A safe, thin, highly conductive solid-state polymer separator for lithium-ion batteries is disclosed. The separator can be deployed in batteries lacking a solvent, allowing lithium ions to pass through channels through the polymerized structure. The lithium-conducting polymer can be formed by free radical polymerization and may include a lithium-conducting polymer having a carbonate solvent, a lithium-conducting material, and a reinforcing additive polymerized between repeat spacers. If desired, an interfacial coating may be present on one or more sides of the separator to ensure long-term operation. The use of such a separator in solid-state lithium batteries may simplify cell assembly, reduce shrinkage, and enhance safety. Various methods for manufacturing solid-state polymer separators for lithium-ion batteries are disclosed.

Description

[Technical Field]

[0001] This disclosure relates to chemistry, i.e., electrical current generating devices. More particularly, this disclosure relates to the manufacture of battery components with certain improvements in separator manufacturing to enhance overall battery performance, safety, and conductivity. [Background technology]

[0002] Lithium-ion batteries, or Li-ion batteries, are a type of rechargeable battery commonly used in portable electronic devices and electric vehicles. Compared to previous battery technologies, lithium-ion batteries offer faster charging, higher capacity, and higher power density, as well as improved performance through smaller and lighter packages. There are many reasons why lithium has become a favored element in battery technology, but the most important reason has to do with its elemental structure. Lithium easily loses its outermost electrons, making it highly reactive and allowing current to flow easily through the battery. Lithium is the lightest metal, making it much lighter than other metals commonly used in batteries (e.g., lead). This property is important for small objects like phones but also for automobiles, which require many batteries. Finally, lithium ions and electrons easily return to the positive electrode (cathode), allowing for numerous recharge cycles. Innovations in lithium-ion battery technology have helped increase the capacity of electronic devices while minimizing their form factors. Smartphones, smartwatches, wearable devices, and other modern electronic luxury items would not be possible without some of the advances in lithium-ion batteries we have seen in recent decades.

[0003] Conventional 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 electrical current during charging and discharging. Electrical current "flows" through the liquid electrolyte between the cathode and anode to allow the battery user to store and use the electrical energy stored in the battery. More specifically, lithium ions move from the negative electrode (cathode) through the electrolyte to the positive electrode (cathode) during discharge and reverse during charging. These lithium-ion batteries typically use an intercalated lithium compound as the material in the cathode and graphite in the anode. Graphite in its fully lithiated state, LiC6, correlates to a maximum capacity of 372 mAh / g.

[0004] Liquid lithium-ion batteries offer high energy density, no memory effect, and low self-discharge, but they contain a flammable electrolyte, posing a safety risk. If damaged and exposed to air or improperly charged, these batteries can lead to or cause explosions and fires. Recalls of removable lithium-ion batteries due to fire hazards are common and costly, and some portable electronic device manufacturers have even been forced to recall expensive electronic devices without removable batteries due to lithium-ion fires. This issue is of growing concern due to the incorporation of liquid lithium-ion batteries in electric vehicles (EVs). Liquid lithium-ion batteries in EVs can easily ignite when exposed to water in the air during or immediately after an accident, posing a major safety concern. This safety issue becomes more important to address as electric vehicles become increasingly commercially viable and more widely adopted.

[0005] Much of the research and development to address these concerns regarding liquid lithium-ion batteries has focused on developing batteries with components that do not contain liquid. In the solid state, lithium has a maximum possible capacity of 3600 mAh / g, nearly 10 times that of LiC6. However, lithium metal is highly reactive even in the solid state and flattens very unevenly. Even in liquid electrolyte lithium-ion batteries, the plating rate is typically low, with a low critical current (0.5 mA / cm²). 2 When the current rate exceeds what is considered normal, lithium can form dendritic or moss-like structures rather than smooth or flat plates. This is the main reason for electrolyte decomposition, swelling, expansion, and even perforation in liquid lithium-ion batteries. In legacy solid-state lithium foil anode batteries, this current rate is even lower (0.1 mA / cm²). 2 ). In legacy solid-state lithium foil anode batteries, this current rate is even lower (0.1 mA / cm 2 Therefore, just as many advances in liquid electrolyte lithium-ion batteries have reduced the possibility of dendritic or moss-like formation, advances in preventing this formation are all the more important when attempting to manufacture solid-state lithium-ion anodes. If the charge-discharge rates are within the same range as what consumers and manufacturers expect from modern liquid lithium-ion batteries, batteries with much larger energy storage capacity will be advantageous. Summary of the Invention [Problem to be solved by the invention]

[0006] Some research and development in solid-state lithium battery technology has focused on developing separators suitable for facilitating solid-state lithium-ion batteries without liquid electrolytes. Separators are typically insulators capable of providing electronic isolation between the battery anode and cathode to prevent internal short circuits between each solid-state component. Fabrication of solid anodes and cathodes requires battery separators with sufficient structure, chemistry, and composition to allow for the incorporation of other solid-state components (e.g., anodes and cathodes). Some separators previously developed for liquid lithium-ion batteries often comprised polymer sheets constructed from polyethylene and / or polypropylene (PE / PP). These sheets offer various porosities (e.g., 35% to 60%). These polymer sheet separators use a filler electrolyte, often containing a lithium salt (e.g., LiPF6) dissolved in an organic solvent (e.g., ethyl methyl carbonate or dimethyl carbonate). Thicknesses vary and can be as thin as 15 μm. Despite their pores, the porous polymer sheet separators developed are typically still "perfect" insulators, meaning they do not conduct lithium ions or electrons but allow their transport across the separator. Instead, lithium ions migrate through a liquid electrolyte that fills the pores of the porous polymer sheet separator. The bulk conductivity of liquid electrolytes in organic solvents is approximately 10 mS / cm at room temperature. However, when they fill an insulating porous polymer sheet separator, the lithium conductivity of the entire separator can decrease by as much as 100x, to values ​​approaching 0.1 mS / cm at room temperature. Furthermore, porous polymer sheet separators undergo areal shrinkage at temperatures as low as 100°C when the anode contacts the cathode during use, with the risk of internal short circuits and thermal runaway. Furthermore, the use of PE / PP separators typically requires the organic solvent in liquid form, which means that they may not be suitable when a solid form factor is desired, for the reasons mentioned above. [Means for solving the problem]

[0007] It is therefore readily apparent that there is a recognized unmet need for improvements in battery separators to enable truly solid state separators for solid state batteries that allow a bulk migration pathway for lithium ions. The present disclosure is designed to address this need through various improvements to the components and internal structures, including the anodes disclosed herein, while addressing at least some aspects of the problems discussed above.

[0008] Briefly, in a preferred embodiment, the present disclosure overcomes the aforementioned shortcomings and fulfills a recognized need for solid-state lithium-ion batteries by introducing various improvements to battery manufacturing, construction, and design for accommodating solid separators within such batteries. These generally include, but are not limited to, the incorporation of novel and / or newly adapted lithium-conducting polymers, solid polymer electrolyte (SPE) composites, and interface coatings, either separately or in combination. By enabling solid-state lithium-ion separators, these improvements have the potential to increase the energy storage capacity of lithium-ion batteries from their theoretical maximum in liquid electrolyte form to a higher-energy-density solid form without sacrificing conductivity throughout the solid separator. Furthermore, these improvements, alone and / or in combination, help reduce the potential for hazards such as fire resulting from swelling, swelling, or damage to lithium-ion batteries. These improvements, alone and / or in combination, may enable these benefits without the associated costs of reduced charging rates, reduced conductivity, added volume or weight, and reduced power delivery to devices.

[0009] One aspect of solid separators for solid-state lithium ion batteries can be the incorporation of novel lithium conducting polymers. Lithium conducting polymers can be produced in a variety of forms, each with corresponding advantages and tradeoffs. These variations in form can be better understood as separate and distinct embodiments of the lithium conducting polymer, or can be used in combination to achieve a balance of advantages and tradeoffs.

[0010] In a potentially preferred embodiment, the lithium-conducting polymer may comprise a polymerized carbonate block (i.e., a polymer derived from the polymerization of a carbonate solvent) rather than a polyethylene glycol-based block (polyethylene oxide or PEO). Carbonate solvents are highly polar and offer higher conductivity for lithium ions. Carbonate solvents also have improved oxidative stability due to the delocalization of free electrons on the carbonyl groups. Therefore, polymer blocks from carbonate solvents such as vinylene carbonate, ethylene carbonate, or propylene carbonate may be preferred over PEO for solid-state lithium-ion separator construction. Furthermore, carbonates may have additional conductivity advantages over PEO. The increased conductivity may lead to numerous benefits related to the use, manufacture, and implementation of high-voltage cathodes (e.g., nickel-manganese-cobalt, nickel-cobalt-aluminum oxide, and / or lithium-cobalt-oxide cathodes). Ether solvents and polymers derived therefrom (such as PEO) are generally incompatible with high-voltage cathodes and can only be used for lower-voltage cathodes (e.g., lithium iron phosphate cathodes). Carbonate-derived polymers promote electron delocalization and have greater oxidative stability, thereby enabling the deployment of these higher-voltage cathode technologies with appropriate separator technology. One exemplary method for polymerizing such carbonate solvents is by polymerizing alkene linkages in the solvent via free radical polymerization. Various improvements to the use of these carbonate solvents in polymerized form, including increased solubility, chemical structure considerations, increased lithium conductivity, and the introduction of spacers and cyclic monomers, will become apparent to those skilled in the art from the following brief description of the drawings, detailed description of exemplary embodiments, and claims, when read in light of the accompanying figures or illustrations.

[0011] Another example of a solid separator for solid-state lithium-ion batteries may be a solid polymer electrolyte (SPE) composite. Solid polymer-based separators may contain lithium-conducting materials with electronic insulating properties. Low material density may be required to produce cells with high energy densities. Generally, the lowest-density solid-state materials manufactured today are polymers with chemical structures (microstructures) that contribute to a low-density macrostructure. Therefore, polymers capable of conducting lithium may be suitable materials for forming the structure for one of these separators in solid-state cells with high energy densities. Lithium conductivity in polymers may be facilitated or enabled by Li+ coordination or conductive sites within the structure with high mobility. Such groups may include silicon-based polymers with ether oxygens, carbonate oxygens, or similar functionalities such as siloxanes. Other Li+ conductive sites on the polymer may be nitrogen-, phosphorus-, or sulfur-based, as found in polydopamines, polyimides, polyphosphazenes, or polysulfonates. A separator having a thickness of less than 20 microns may be preferable because it may enable both a free-standing structure and stability in moist air. Fabrication of such a structure may also contribute to easy adoption by the existing battery industry. A problem that has hindered the adoption of such separator materials in the battery industry is that polymers with high lithium conductivity generally have short chains, which may prevent them from forming thin, free-standing films. The strength modulus of these lithium-conducting polymers may be improved by blending them with inorganic materials to create composites. These inorganic materials may desirably share the lithium conductivity and low density properties. Such inorganic additives include 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 Cl0.3 ), LGPS(Li 10 GeP2S 12 ), or conductive halides and closo- / nido-borates of lithium. Electronically insulating carbon-based additives and clays can also be used. Finally, it can be important that the inorganic additive remain as a small fraction of the composite, such as less than 10% of the total separator by weight, volume, and / or mass.

[0012] In certain various potentially preferred embodiments of this model, various manufacturing techniques and standards may be important for the production of both solid separators and solid-state lithium-ion batteries. These include electrospinning of conductive polymers and SPEs, and blade casting of conductive polymers and SPEs. Those skilled in the art will understand that certain polymers, certain SPEs, and certain combinations thereof may require one or a combination of these techniques. A brief description of the drawings, a detailed description of the exemplary embodiments, and the claims below will become more apparent to those skilled in the art when read in reference to the accompanying drawings or illustrations, showing various improvements to the introduction of conductive polymers into SPEs.

[0013] In yet another aspect of solid separators for solid-state lithium-ion batteries, lithium conductivity can be maximized throughout a thin (less than 20 microns) solid separator, so the separator may include one or more interfacial coatings. At this thickness, the interface with the anode or cathode may require additional processing to ensure long-term operation. This can be a significant issue for stability, longevity, 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 polymers 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 interfacial coating will become more apparent to those skilled in the art upon reading the following brief description of the drawings, detailed description of exemplary embodiments thereof, and claims in light of the accompanying figures or illustrations.

[0014] Generally, various aspects and features of solid separators for solid-state lithium-ion batteries, alone or in combination with features associated with solid-state lithium-ion batteries, are superior to conventional liquid electrolyte lithium-ion batteries and existing, available, experimental, and / or proposed solid-state lithium-ion batteries and their respective separators. An advantage of solid separators for solid-state lithium-ion batteries may be their ability to increase the energy density of the battery over currently commercially available batteries with liquid cells. Another advantage of solid separators for solid-state lithium-ion batteries is their ability to increase the energy density of the battery over the 0.1-0.5 mA / cm currently observed for solid-state batteries. 2 Exceeds 10mA / cm 2Another feature of solid separators for solid-state lithium-ion batteries may be their ability to enable high operating currents approaching 1000 volts per minute. This could have commercially significant implications for charging high-energy density batteries in less than 30 minutes. Another feature of solid separators for solid-state lithium-ion batteries may be their ability to enable safe lithium-metal battery construction with lithiophilic interfaces that result in high cycle life (e.g., greater than 4000 cycles), which may be commercially important for electric vehicles and other durable goods requiring long installed battery life. Another feature of solid separators for solid-state lithium-ion batteries may be their ability to operate over a much 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 separators for solid-state lithium-ion batteries may be their ability to allow for pre-lithiated anodes during manufacturing. Another feature of solid separators for solid-state lithium-ion batteries may be their ability to enable the fabrication of bipolar cells. Bipolar cells utilize a bipolar current collector with an anode on one side and a cathode on the other. This may not be possible otherwise and is not known to be possible with liquid-containing separators, as the liquid would flow between the stacks, causing ionic shorts and decomposing the electrolyte. Liquid-free, solid separators enable bipolar cells, one factor that may enable higher charge rates due to the lower internal resistance of the overall bipolar cell. Bipolar cells may also be safer for many reasons, including less cell Joule heating during operation. Another feature of solid separators for solid-state lithium-ion batteries is that, in some embodiments, they may be polymer / inorganic composites that may contain flame retardants, which are not flammable and are safer than liquid-containing separators. Another feature of solid separators for solid-state lithium-ion batteries may be that they allow other components of the battery to be solid-state lithium-ion (e.g., solid anode, solid cathode).Finally, various other characteristics of solid separators for solid-state lithium ion batteries include, by way of example and not limitation, additional potential benefits of low density and lightweight materials, high energy density, ability to be manufactured in sheets with large surface area, ability to be manufactured in virgin air, high electrochemical stability, high solvation ratios of lithium per weight or mole ratio, high stability of lithium at the interface with the anode / cathode, high strength, and / or combinations thereof.

[0015] These and other features of the solid separator for a solid-state lithium ion battery will become more apparent to those skilled in the art from the foregoing summary, brief description of the drawings, detailed description of exemplary embodiments, and claims, when read in light of the accompanying drawings or illustrations. [Brief explanation of the drawings]

[0016] The solid separator for a solid-state lithium-ion battery will be better understood from the detailed description when read in conjunction with the accompanying drawings, which are not necessarily drawn to scale and in which like reference numerals indicate like structure and refer to like elements throughout.

[0017] FIG. 1 is a perspective view of a portion of an exemplary embodiment of a high energy density lithium metal-based battery for a solid-state lithium ion battery of the present disclosure.

[0018] Figure 2 shows the components of a conventional battery.

[0019] Figure 3 is a partial perspective view of an exemplary embodiment of a solid separator for solid-state lithium-ion batteries.

[0020] Figure 4 is a block diagram of the battery.

[0021] It should be noted that the drawings presented are for illustrative purposes only, and as such, they are not desired or intended to limit the disclosure to any or all of the precise details of the constructions shown, except as deemed essential to the claimed disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0022] In describing exemplary embodiments of solid separators for solid-state lithium-ion batteries of the present invention, as shown in FIGS. 1-5, specific terminology is used for clarity. However, the present disclosure is not intended to be limited to the specific terminology so selected, and each specific element should be understood to include all technical equivalents that operate in a similar manner to achieve a similar function. However, the claimed embodiments may be embodied in many different forms and should not be construed as limited to the embodiments described herein. The examples described herein are non-limiting examples and are merely examples among other possible examples. Note that the terms battery, cell, anode, cathode, and separator, in their singular and plural forms, are used in reference to the high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries of the present disclosure, as well as in describing other batteries, including, but not limited to, lithium-ion batteries with liquid electrolytes. While a single battery cell is described herein, those skilled in the art of battery manufacturing will understand that multiple cells can be used in the design, construction, manufacturing, and assembly of a battery, and that multiple batteries can be arranged and / or installed within a finished product. Fibre skeleton and fibre sheet are used consistently throughout the detailed description, but may also be understood as fibrous battery skeleton and separator microstructure, respectively.

[0023] 1-5, by way of example and not limitation, there are illustrated embodiments of a high energy density lithium solid-state anode 111 for a solid-state lithium ion battery, as well as a solid separator 131 for a solid-state lithium ion battery. The solid-state battery 100, the liquid electrolyte battery 200, and the battery 300 may be referred to herein simply as batteries. The solid separator 131 for the solid-state lithium ion battery and the porous separator 231 may be referred to herein simply as separators. The high energy density lithium metal-based solid-state anode 111, the liquid electrolyte anode 211, and the anode 311 may be referred to herein simply as anodes. While variations in structure, design, composition, chemistry, and assembly may apply to the cathode 312, for clarity and consistency throughout FIGS. 1-5, any reference to the cathode 312 will be referred to simply as the cathode, and other relevant features may be referenced in the description as they relate to the solid-state battery 100, the liquid electrolyte battery 200, and the battery 300. The solid-state battery 100, the liquid electrolyte battery 200, and the battery 300 may be charged via a charger 351 and discharged to a power receiving device 352. As described herein, the solid-state battery 100, the liquid electrolyte battery 200, and the battery 300 may each have a single cell or may have multiple cells connected and / or assembled with multiple layers of anode 311, cathode 312, and separator 331. Lithium, lithium metal, elemental lithium, and lithium ions are referred to interchangeably herein, and the present disclosure is not limited to batteries having lithium metal as its electrical flow element. Other elements may include, but are not limited to, zinc, sodium, cobalt, nickel, lead, potassium, other metals, salts thereof, etc., and / or combinations thereof.

[0024] In one exemplary embodiment that may be preferred, solid-state battery 100 may include the following components: a solid-state anode 111 having a solid electrolyte 112 with a fibrous framework and shown with metal ion deposits 120, a solid separator 131, and a cathode 312 having a solid cathode current collector 132. In an embodiment of liquid electrolyte battery 200, 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 battery 300, battery 300 may include the following components and connections: anode 311, cathode 312, separator 331, charger 351, and power receiving device 352.

[0025] Referring now more specifically to FIG. 1, shown therein is an example of a solid-state battery 100. Starting towards the top is a solid-state anode 111 having solid separators 131 both above and below the solid-state anode 111. The solid-state anode 111 may be formed from one or more layers of solid electrolyte 112, each layer of solid electrolyte 112 may be formed from a fibrous framework. Generally, the solid-state anode 111 transfers electrons to an external circuit (see FIG. 4). The cathode 312 may be understood as a negative or reducing electrode that releases electrons and is oxidized during the electrochemical reaction. The cathode 312 may be understood as a positive or oxidizing electrode that gains electrons from an external circuit (see FIG. 4) and is reduced during the electrochemical reaction. In this potentially preferred embodiment, the solid-state anode 111 may include a solid electrolyte 112, which may be understood as a skeleton of interconnected fibers. The solid-state anode 111, being a skeleton of interconnected fibers, may have a variety of properties and may be flexible or rigid. In the case of a ceramic fiber skeleton, ceramic may be utilized to provide structure, support to the solid-state anode 111 and solid-state battery 100, and a surface onto which lithium or other metals may be deposited. The lithium metal in the metal ion deposit 120 may provide electronic conductivity for the solid-state battery 100, while the solid ceramic framework / skeleton may provide volume support, a surface layer for the metal deposit 120, and lithium ion conductivity. During charging and discharging of the solid-state battery 100, the metal deposits 120 grow in size toward the solid separator 131 and shrink toward the center of the solid-state anode 111. One means of bonding, fabricating, and / or operably engaging the metal ion deposits 120 with the fibrous skeleton of the solid electrolyte 112 can be melt infusion of lithium metal into a processed ceramic skeleton. Initially, only a small amount of lithium metal is required to infuse the pre-cell assembly of the solid-state anode 111. In such cases where only a small amount is infused into the pre-cell assembly of the solid-state anode 111, most or all of the reversible lithium that provides the cell with its capacity can come from the cathode 312 in the final assembly. Thus, during the first charge and all subsequent charges of the solid-state battery 100, the metal ion deposits 120 can be detected or observed to be very small at or near the center of the solid-state anode 111.During the charging process of the solid-state battery 100, the metal ion deposits 120 can be detected or observed to grow in size outward toward the solid separator 131 and along the solid electrolyte 112, even to the point of occupying all of the space within the fibrous skeleton of the solid-state anode 111. Deposition of lithium and / or other metals can also occur through the temporary use of high-voltage insertion cathodes, such as lithium ferrophosphate (LFP), lithium cobalt oxide (LCO), nickel / manganese / cobalt (NMC), and / or various cathode combinations thereof. The greater surface area of ​​the solid electrolyte 112 with a ceramic fibrous skeleton can result in higher operating speeds (lithium plating / stripping) of the solid-state battery 100 compared to flat lithium foils. However, flat lithium foils can also be used as the initial form of the metal ion deposits 120, or they can be melt-injected along the center of the solid-state anode 111 within the solid electrolyte 112.

[0026] From the standpoint of energy density, a key requirement for the ceramic fiber skeleton of the solid electrolyte 112 may be the use of low-density ceramics. A proposed example of a low-density lightweight ceramic is Li 1+x Al x Ti 2-x P3O 12(LATP). In this embodiment of the solid-state anode 111 having a ceramic-containing solid electrolyte 112, further variations may exist, including additional components, manufacturing methods, and various advantages and trade-offs. These may include the selection of active material and functional material treatment types. In a potentially preferred embodiment of the ceramic version of the solid electrolyte 112, a coating material having qualities that attract specific metals may offer the increased advantage of facilitating smooth and consistent plating along the internal fibrous skeleton. These may include an engineered solid-state anode 111, which has a solid electrolyte 112 having a total thickness per layer of about 80-90 μm, a total length and width of about 5 cm × 5 cm along the solid separator 131, a porosity of the internal fibrous skeleton of more than 70%, individual and / or average fiber diameters of less than 0.35 μm, individual and / or average fiber lengths of more than 1 mm, a coating thickness of about 10 nm, and a coating material comprising oxides, nitrides, polymers, or ceramics. Oxide coating materials for fibers in the solid electrolyte 112 include, but are not limited to, niobium, Al2O3+ZnO(AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur oxides, and / or combinations thereof. Nitride coating materials for fibers in the solid electrolyte 112 include, but are not limited to, boron, vanadium nitride, and combinations thereof. Polymer coating materials for fibers in the solid electrolyte 112 include, but are not limited to, succinonitrile (SCN). Ceramic coating materials for fibers in the solid electrolyte 112 include, but are not limited to, crossoborate (CB), lithium oxynitride phosphate (LiPON), and / or combinations thereof. By using one or more coatings on the ceramic fiber structure of the solid electrolyte 112, the bonding of ceramics that do not readily bond to lithium or other metals to lithium is facilitated, thereby allowing the solid metal, including lithium ions, to act as an electrolyte over which solid metals can move freely during charging and discharging.

[0027] In a second possible preferred embodiment of the lithium conductor side of the solid-state anode 111 for the solid-state battery 100, a polymer backbone in the solid electrolyte 112 is preferred. The polymer backbone of the solid electrolyte 112 in the solid-state anode 111 can offer the additional advantage of being flexible, while the previous ceramic fiber backbone of the solid electrolyte 112 in the solid-state anode 111 can be described as rigid. This can offer various advantages and trade-offs at both the individual cell level or the layer level of the solid-state battery 100, but it can also offer various trade-offs and advantages to the power receiving device 352 in which the solid-state battery 100 is installed. The requirements for the polymer backbone of the solid-state anode 111 and the material deposited therein are: (a) having a melting point above the melting point of lithium metal (180°C), (b) being nonconductive to lithium ions, and (c) a corresponding lithium salt (e.g., lithium bis(trifluoromethanesulfonyl)imide / LiC2F6NO 4sLithium-conducting materials, such as other conductive polymers with a crystalline structure (e.g., Li2SO4 / LiTFSI) or ceramic particles embedded in and / or on the surface of a polymer, may be infused into the structure of the solid electrolyte 112. This embodiment of the solid-state anode 111 with a polymer skeleton of the solid electrolyte 112 may have additional components, manufacturing methods, and further variations with various advantages and tradeoffs. These may include a fiber mat extending throughout the solid-state anode 111 and solid electrolyte 112, which may further include aramid and polyimide frames. Furthermore, not all coatings for ceramic fiber skeletons are applicable to polymers or polymer fiber skeletons, and not all properties and characteristics of ceramic fiber skeletons are directly applicable to polymers or polymer fiber skeletons, although some may be. These may include engineering solid-state anodes 111. It has a solid electrolyte 112 with a total thickness per layer of about 80-90 μm, a total length and width of about 5 cm x 5 cm along the solid separator 131, an internal fiber skeleton porosity of greater than 70%, individual and / or average fiber diameters of less than 0.35 μm, individual and / or average fiber lengths of greater than 1 mm, a coating thickness of about 10 nm, and a coating material including an oxide, nitride, polymer, or ceramic. Oxide coating materials for the fibers in the solid electrolyte 112 include, by way of example and not limitation, niobium, Al2O3 + ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur oxides, and / or combinations thereof. Nitride coating materials for the fibers in the solid electrolyte 112 include, by way of example and not limitation, boron, vanadium nitride, and the like, and combinations thereof. Polymer coating materials for the fibers in the solid electrolyte 112 include, by way of example and not limitation, succinonitrile (SCN). Ceramic coating materials for the fibers in the solid electrolyte 112 include, by way of example and not limitation, closoborate (CB), lithium phosphate oxynitride (LiPON), and the like, and / or combinations thereof.The use of one or more coatings on the ceramic fiber structure of the solid electrolyte 112 promotes the binding of lithium to ceramics that do not readily bind to lithium or other metals, thereby allowing the ceramic to act as an electrolyte over which solid metals, including lithium ions, can move freely during charging and discharging.

[0028] The initial deposition of lithium, included in potentially preferred embodiments of either the ceramic fiber skeleton or the polymer fiber skeleton of the solid-state anode 111 and solid electrolyte 112, can be important for several reasons. These may initially form in very small, almost impractical amounts in the metal ion deposits 120, but may grow in size, weight, and volume, and even occupy all of the free space within the solid-state anode 111 and solid electrolyte 112. This can be achieved through a variety of means, but a potentially preferred process for initially depositing the metal on the surface of the solid electrolyte 112 and its fibers, near the center of the solid-state anode 111, and its fibers may be via melt injection of lithium foil.

[0029] Furthermore, the fabrication of the fibers themselves, whether ceramic or polymeric, can offer a variety of important improvements to the structure, formation, and overall properties of the solid electrolyte 112, solid-state anode 111, and solid-state battery 100. These techniques may have little to no known applications in the battery technology industry, but may have significant applications in the materials science and nonwoven materials industries. One such process involves a sol-gel process, which preferably occurs prior to the deposition of the metal ion deposit 120. This chemical process can form a "sol" (colloidal solution), which then gradually progresses toward the formation of a gel-like two-phase system containing both liquid and solid phases and with a morphology ranging from discrete particles to a continuous polymer network. In the case of colloids, where the particle volume fraction is low, a significant amount of fluid may need to be initially removed for gel-like properties to be recognized. One such means of liquid removal is simply to allow time for settling to occur, and then pour off the remaining liquid. Centrifugation can also be used to accelerate the phase separation process. Removal of the remaining liquid (solvent) phase requires a drying process, which can result in significant shrinkage and densification. The rate at which the solvent can be removed ultimately depends on the porosity distribution within the gel. The final microstructure of the final component can be strongly influenced by the changes imposed on the structural template during this stage of processing. A heat treatment or calcination process is often required to promote further polycondensation and enhance mechanical properties and structural stability through final sintering, densification, and particle growth. One distinct advantage of using this methodology, as opposed to more traditional processing techniques, is that densification is often achieved at much lower temperatures. The precursor sol can be deposited onto a substrate (e.g., by dip coating, spin coating, or electrospinning) to form a film, cast into a suitable container with a desired shape (e.g., to obtain monolithic ceramics, glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres). This technology, when combined with electrospinning, is known to produce paper-like materials with open cavities that are highly suitable for the deposition of metals, i.e., lithium ions.Using the various compositions of the disclosed ceramics and polymers, additional processes that can further enhance this space-filling and open-cavity characteristic of the solid electrolyte 112 can include co-precipitation, evaporation and self-assembly, and the use of nanoparticles.

[0030] In any embodiment of the solid electrolyte 112, whether ceramic or polymer, materials in which the fibrous structure has an open cavity, or materials in which the fibrous structure has a lithium-parent coating, can be considered active materials, and the solid-state anode 111 includes such materials. In other words, the active material of the solid-state anode 111 may be the solid electrolyte 112, which is an active material through which lithium ions migrate and aggregate in the metal ion deposit 120. Any active material manufactured to produce the solid-state anode 111 may have these properties and be processed into a functional material that acts as the solid electrolyte 112 of the solid-state battery 100. The first step of this process may be the synthesis of a fibrous mat containing materials such as LATP, closoborate, and sulfide ceramics. The sol-gel or other process steps for forming the open cavity structure of the solid electrolyte 112 can be improved by reducing the firing temperature required by performing aliovalent substitution. Other improvements include maximizing density by using 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 of the solid electrolyte 112, the active material of the pre-assembled solid electrolyte 112 may need to be obtained to obtain a robust functional laminate, sheet, or mat for use as a solid-state anode 111. Slurry additives may be added to process the green laminate during the 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 of green materials using traditional techniques known to those skilled in the art may be a long process (more than 10 hours) and may need to occur at high temperatures (more than 1250°C). These conventional requirements may necessitate high operating costs, difficulties in scaling up, and undesirable lithium losses due to evaporation during sintering.The loss of lithium at these times and temperatures may need to be addressed by using extra lithium salts during synthesis, which would only further increase costs. Instead, a method should be substituted that allows for scalable application in open air and prevents lithium loss or consumption. The resulting sintered green laminate should contain voids for lithium metal melt injection following sintering, which can occur at room temperature. The resulting solid electrolyte 112 is suitable for lithium deposition along with the metal ion deposit 120.

[0031] Alternative means for promoting these properties within the solid electrolyte 112, thereby creating an optimal solid-state anode 111, include, but are not limited to, reactive sintering of starting materials, sintering in an electric field, microwave sintering, SPS or spark plasma, cold sintering using solvent evaporation and salt CSP, and flash sintering using high currents. Alternatively, or in combination with these techniques for developing the solid electrolyte 112, porous sheets can be fabricated using sacrificial beads—various plastics or carbons with low vaporization temperatures that can be removed and / or destroyed to leave openings in the fiber mat—or by developing ceramic fiber mats via electrospinning. Other means considered for specific application to polymer fiber versions of the solid electrolyte 112 include the use of polymers with the melting point of lithium metal (180°C). However, these polymers typically do not conduct lithium ions, so additional lithium-conducting materials can be infused into the structure, such as other conductive polymers (with corresponding lithium salts, such as LiTFSI) or ceramic particles, to serve as a structural component. Further examples include aramid and polyimide frames. Yet another example that provides a suitable formulation for the solid electrolyte 112 may be a hybrid composite structure having both polymeric and ceramic fiber properties. The hybrid composite fiber mat includes fumed silica and G4 / LiTFSA with boron / vanadium (or other nitride) doping on the surface.

[0032] Even more important to the surface structure and composition of the solid electrolyte 112 may be coating alternatives that, alone or in combination, may provide additional benefits to the deposition, mobility, and smooth plating of the metal ion deposit 120. These include CVD / PVD / PECVD and / or ALD deposition in combination with AZO deposition; the use of I2, Li3N, Li3PO4, LLZO, Li9AlSiO8, Li3OCl, LiI:4CH3OH; or the use of metals that alloy well with lithium, including, but not limited to, aluminum, indium, zinc, magnesium, silicon, and / or gold. Solution coatings may also be used on the solid electrolyte 112 or form its critical components, which may be developed using sulfur-based solution coating methods, such as with solutions of polysulfides, dissolved sulfur ZnO-doped argyrodite Li6PS5Br, Li2S3, or Li3S4, dissolved in DEGDME. Polymer coatings can additionally be used as surface coatings on the solid electrolyte 112, including elastomers such as SN / FEC, SHP with additives and salts (e.g., CsPF, CsTFSI, LiNO, LiF, CuF), and even adhesives such as polydopamine and / or polysiloxane. These various coatings on the solid electrolyte 112 offer various advantages, including reduced dendritic growth of lithium in the metal ion deposit 120 and during plating on the solid electrolyte 112, a wider range of possibilities for solid electrolyte 112 compositions for various applications, and prevented reactions between various highly useful materials for construction of the solid-state anode 111 and lithium or other metals.

[0033] Alternatively, it is contemplated herein that the metal ion deposit 120 can be replaced by an anode current collector disposed within the solid-state anode 111 within the solid electrolyte 112. These include foils or films onto which metals, particularly lithium, are deposited. Exemplary materials for the anode current collector disposed within the solid-state anode 111 within the solid electrolyte 112 include, but are not limited to, vanadium nitride, lithium-aluminum alloys, liquid metals including gallium, indium, tin, and the like, and / or combinations thereof.

[0034] 2, shown therein is an example cross-sectional view of a cell of a liquid electrolyte battery 200. Generally, a conventional lithium-ion battery 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 embodiments of lithium-ion batteries with liquid electrolytes may achieve capacities of 275 Wh / kg and have rechargeability, but suffer from significant drawbacks as discussed in the Background section above.

[0035] If sufficient open space is achieved while maintaining the structure, lithium smooth plating, and other considerations described herein, the solid-state battery 100 may achieve substantially higher capacities while enabling additional benefits such as durability, safety, fast charging, and other aforementioned benefits. For example, the 275 Wh / kg capacity of the liquid electrolyte battery 200 compares favorably with the solid-state battery 100 of the present disclosure, which has achieved over 635 Wh / kg in various configurations and combinations.

[0036] Up to this point, various exemplary and suitable solid-state anodes for solid-state lithium-ion batteries have been described. Now, referring specifically to Figure 3, a perspective view of a portion of exemplary embodiments of a solid separator 131 for a solid-state lithium-ion battery is shown. Broadly speaking, the solid separator 131 for a solid-state lithium-ion battery can be formed from one or more sheets, each sheet having a microscopic structure characterized by various improvements and features described herein. These may include, but are not limited to, a main polymer 520 (shown as the thicker of two groups of long fibers throughout the solid separator 131), a structural polymer 530 (shown as the thinner of two groups of long fibers throughout the solid separator 131), and a reinforcing additive 510 (shown as a group of circles throughout the solid separator 131). Each face of the solid separator 131 may have its own or distinct features, qualities, chemical composition, etc., and / or combinations thereof, but it should be understood that the top face 313 and bottom face 113 may be considered to have features that are not clearly defined in this disclosure. Nevertheless, the top face 313 should operably engage with the cathode 312, and the bottom face 113 will operably engage with the anode 311 (or liquid electrolyte anode 211). This does not mean that the bottom face 113 can operably engage with the cathode 312 or the top face 313 can operably engage with the anode 311, but simply that the anode is on the opposite side of the solid separator 131 from the cathode. Figure 3 is not drawn to a certain scale and does not explicitly depict the microscopic appearance or structure of the solid separator 131, but depicts an exemplary figure to further demonstrate the purpose, structure and formation of the solid separator 131. Furthermore, those skilled in the art will understand the cross-sectional properties of the illustration in Figure 3 and realize that it may represent only a small fraction of the materials that may be required even in a single-cell solid-state lithium-ion battery. The thickness of the solid separator 131 can be understood to be generally uniform, although at a microscopic level, a thickness gradient may be evident. The solid separator 131 can be understood to be very thin, have a large surface area, and be low in density.Other objective qualities of the solid separator 131 are understood and described herein.

[0037] Returning now to the basic structural and chemical composition of solid separator 131, as shown in FIG. 3, there is now described a primary polymer 520, a structural polymer 530, and a reinforcing additive 510.

[0038] The primary polymer 520 can overlap across the length, width, and depth of the solid separator 131, as shown in FIG. 3, and can be understood as generally and / or uniformly distributed throughout the solid separator 131. As mentioned above, conventional lithium-conducting polymer electrolytes may be polyethylene oxide (PEO)-based. Electrolytes of this family require temperatures above 45°C to provide conductivities greater than 0.1 mS / cm, typically around 60°C. For proper industrial adoption, a wider temperature range is required to provide similar conductivities. PEO is a polymerized version of ether solvents known to conduct lithium ions. Ether solvents are not used in liquid cells because their low polarity reduces lithium ion conductivity. In other words, PEO polymers inherit the drawbacks of their monomeric components. 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 primary 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 the respective polymers, as do combinations of these carbonates as monomers in the carbonate polymer sequence. Furthermore, due to their ability to allow electron delocalization, the exemplary solid separator 131 containing a polymer derived from a carbonate can provide the added benefit of increasing the allowable voltage of the cathode 312 beyond that possible with a PEO-based separator. Carbonates can be polymerized via various chemical reactions, such as the exemplary chemical reaction of polymerizing alkene bonds in a solvent via free radical polymerization.

[0039] A variety of specific representative polymers for the main polymer 520 are described herein, each of which can be used alone or in combination in the solid separator 131. Important to each candidate polymer for the main polymer 520 is the concept of a spacer monomer. Vinylene carbonate (VC) has the highest conductivity for lithium ions and is therefore an important candidate block material for the main polymer 520. However, due to its ring structure, it is highly rigid when polymerized, making the resulting vinylene carbonate polymer very low in lithium conductivity. To increase the chain flexibility and ultimately the lithium ion conductivity, a series of "spacer" linear monomers can be inserted between the bulky VC cyclic monomers. Such "spacer" linear monomers can be diol acrylates (e.g., butanediol and hexanediol) or glycol acrylates (e.g., triacrylates, diacrylates, and monoacrylates). Because the solubility of these molecular combinations in solution can be challenging, the solubility of these materials can be improved by adding a small molar ratio of a highly polar epoxy oxirane (e.g., glycidyl acrylate). The oxirane can be polymerized with low-boiling amines in untreated air after assembly to increase separator strength. Removal of excess unpolymerized initiators or polymerization reactants, such as azobisisobutyronitrile (AIBN) or amines, can be important for maximizing cycle life and improving battery operation. Left unremoved, these highly reactive materials can accelerate battery degradation. Therefore, it is important to utilize a polymerization mechanism to reinforce the separator with low-boiling reactants, allowing any excess to be easily evaporated during the drying process. In summary, this polymer candidate can be understood in its basic ternary building block as spacer + VC + oxirane.

[0040] Other such polymer candidates for the primary polymer 520 can be understood as other basic ternary components, such as spacer + prop-1-ene 1,3-sultone (PES) + oxirane, spacer + 4-vinyl-1,3-dioxolan-2-one + oxirane, spacer + allyl methyl carbonate + oxirane, and polyacrylonitrile (PAN) + succinonitrile (SCN). Specifically, succinonitrile (SCN) can be an important additive to the primary polymer 520 due to its properties as a highly conductive wax for lithium ions in its polymeric state. SCN can be added to the solid separator 131 in various ratios to improve its conductivity, if necessary. For example, the low conductivity of PAN can be increased by a small proportion of SCN.

[0041] The structural polymer 530 can overlap the length, width, and depth of the solid separator 131, as shown in FIG. 3, and may be understood to be generally and / or uniformly distributed throughout the solid separator 131. Perhaps the most important, or even critical, properties for the solid separator 131 are (i) lithium conductivity and (ii) electronic insulation. An additional property that may be beneficial, if not critical, may be low material density, which may be required to produce a high-energy-density cell. As noted above, the lowest-density solid materials are polymers, making lithium-conducting polymers excellent candidates for the solid separator 131 to provide the framework for the solid-state cell and impart its high-energy-density properties. Lithium conductivity in polymers is provided by highly mobile Li+ coordination sites. Such groups may include ether-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, such as those found in polydopamine, polyimide, polyphosphazene, or polysulfonate. Preferably, the overall thickness of the solid separator 131 should be less than 20 microns thick. The solid separator 131 must also be free-standing and stable in humid air. These requirements, in addition to benefiting the overall usefulness and functionality of the solid separator 131, may facilitate the adoption of the solid separator 131 and solid-state batteries in general by battery manufacturers in various markets. Polymers with high lithium conductivity generally have short chains and therefore may not form thin, free-standing films by themselves. Their strength modulus can be improved by blending with inorganic materials, such as the reinforcing additive 510, to create a composite. It is desirable that these inorganic materials, including the reinforcing additive 510, in addition to the main polymer 520 and the structural polymer 530, also be lithium conductive and have low density. Such inorganic additives, which may include the reinforcing additive 510, may be LATP, LLZO, LSPSCl, LGPS, lithium conductive halides, closo- / nido-borates, and the like, and / or combinations thereof.Electronically insulating carbon-based additives can also be used to form the reinforcing additive 510. Whether inorganic or carbon-based, it may be important that the reinforcing additive 510 remains as a small part of the composite while remaining useful for its strengthening purpose. The exemplary amount of the reinforcing additive 510 may be less than 10%.

[0042] The method of combining the primary polymer 520, structural polymer 530, and reinforcing additive 510, or any two thereof, can be important in affecting the overall utility, structure, function, and use of the solid separator 131. An exemplary method of combining the primary polymer 520, structural polymer 530, and reinforcing additive 510 may be electrospinning, which may be understood as a method of combining polymer and inorganic materials into a composite or forming a polymer / inorganic composite. Fabricating the solid separator 131 by electrospinning and / or sintering the inorganic component to the polymer component may be understood to produce a highly porous mat (i.e., a fiber mat with a porosity greater than 90%), which may then be infused with a conductive polymer. Those skilled in the art of nonwoven material fabrication will understand that laboratory-scale electrospinning can generally be performed by applying a high voltage between a metal syringe needle and a conductive plate. Electrospinning may be a more adaptable fiber spinning technique than traditional melt spinning. Electrospinning can be performed via a room-temperature process, producing either randomly aligned or well-aligned fiber mats, depending on the desired mat structure. The fiber mat produced via this process can then remain unreactive at room temperature and exposed to ambient air. When using the needle electrospinning method, hollow-core fibers can even be obtained by using a coaxial needle. This approach can further reduce the weight of the solid separator 131. Unfortunately, there are currently no known methods for scaling up this well-known experimental procedure. However, vis-colloids can be modified following the same principles to rotate fibers under voltage via a rotating conductive spiral without the use of a needle. Using a vis-colloid modified to rotate fibers under voltage via a rotating conductive spiral without the use of a needle could potentially 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), aramid (polymer), and / or combinations thereof.The utilization of modified bis-colloid technology using these exemplary materials can be important for the scalable manufacture of electrospinning of the primary polymer 520, the structural polymer 530 and the reinforcing additive 510, or a combination of any two thereof, to form a solid separator 131 in a solid porous mat.

[0043] Methods of combining the main polymer 520, the structural polymer 530, and the reinforcing additive 510, or any combination of any two thereof, may include blade casting for forming the solid separator 131. By blade casting polymer, inorganic, and / or lithium salt mixtures, those skilled in the art can form a robust, porous fibrous mat having the lightweight properties described herein, suitable as a solid separator 131. Blade casting has the further advantage of being an already scalable process, which is also a conventional process already known in the battery industry. For example, virtually all battery electrodes can be assembled by this technique. The blade casting method of this mixture can offer more advantages in solid separators 131 containing polymer blends to achieve desired strength at the required thickness. However, if the majority of the constituent composition of the solid separator 131 is a polymer composition, and if this polymer composition is also self-supporting, it may be difficult to obtain a thin (less than 20 microns) large-area solid separator 131. Alternatively, this method may be more suitable for a complete layering cell assembly procedure in which the solid separator 131 is layered on top of the electrodes of a complete in-house multi-cell battery assembly from top to bottom. In this case, the assembly can occur simultaneously with the manufacture of the solid separator 131, so the above-mentioned self-supporting requirement is not necessary. Several materials that can be used as components of the blade-cast slurry for manufacturing the solid separator 131 include, but are not limited to, fumed silica (inorganic additive) + G4 (tetraglyme, solvent) and / or LiTFSA (Li salt), LiBOB, LiTFSI, LiBF2(C2O4), LiBF2(C2O4), C2O4Li2, CF3CO2Li, C6H5COOLi, other lithium salts, and / or combinations thereof.

[0044] In addition to the combination of the primary polymer 520, structural polymer 530, and reinforcing additive 510, or a combination of any two thereof, via electrospinning or blade casting to form the solid separator 131, it may further be important to provide an interfacing coating at the interface with the anode 311 or cathode 312 to enable and / or improve the solid-state battery 100. Because it may be desirable to maximize lithium conductivity across a thin (less than 20 microns) solid separator 131, additional processing may be required on the top surface 313 and / or bottom surface 113 of the solid separator 131 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 further processing to ensure long-term operation, durability, and sustainability of the solid-state battery 100. This can be a particularly serious problem at the interface with exposed lithium metal of the solid-state anode 111. An interfacial coating may generally be applied, formed, or otherwise present on the top surface 313 and / or bottom surface 113. Exemplary coatings that may stabilize and promote this interface include, but are not limited to, graphite / graphene (i.e., carbon), nitrides / borates (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 their salts dissolved in solution), sulfur (e.g., Li2SS, LPS), or FEC (i.e., fluoroethylene carbonate, a cathode stabilizer additive).

[0045] Referring specifically to Figure 4, the diagram shows a simple block diagram for a battery 300 having an anode 311, a cathode 312, a separator 331, a charger 351, and a power receiving device 352. When the cathode 312 is in conductive contact with the charger 351, a circuit is formed with the anode 311, thereby charging the battery 300. Alternatively, when the cathode 312 is in conductive contact with the power receiving device 352, a circuit is formed with the anode 311, supplying power to the power receiving device 352. Both charging and power supply occur via 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 anode 111 of the solid-state battery 100 as described herein, the components and features of the battery 300 may be required to fully manufacture and use the solid-state battery 100. Furthermore, various improvements to the components of the battery 300, known and developed in the art of battery manufacturing, including the manufacture of the solid-state battery 100, can further enhance the advantages of the solid-state anode 111 described herein. It is not sufficient to simply replace the anode 311 with the solid-state anode 111; those skilled in battery design and manufacture may implement and adapt the features of the solid-state anode 111 to the battery 300 to fully utilize the disclosure herein.

[0046] With respect to the above description, it should be understood that optimal dimensional relationships include variations in size, material, shape, form, location, function and method of operation, assembly, anode / cathode / battery container type, connection type, and use, all of which are intended to be encompassed by the present disclosure. It is contemplated that the solid-state anode 111, solid separator 131, and various parts and components described herein for a high-energy-density lithium metal-based anode, or solid-state lithium-ion battery (solid-state battery 100), can include various overall sizes and corresponding sizes of various parts, including, but not limited to, the solid-state anode 111, solid electrolyte 112, metal ion deposit 120, solid separator 131, cathode 312, cathode current collector 132, etc., and / or combinations thereof. Indeed, these various parts and components of solid-state battery 100 may change in size, shape, etc. during standard operation of solid-state battery 100. While the description of the high-energy-density lithium metal-based solid-state anode 111 for solid-state battery 100 in combination with solid separator 131 herein refers to benefits for electric vehicles and other electronic devices, the invention is not so limited. The presently disclosed solid separator 131 for solid-state lithium ion batteries and batteries produced therefrom may have applications for powering other vehicles, computers, businesses, homes, industrial facilities, consumer and portable electronics, hospitals, factories, warehouses, government facilities, data centers, emergency backup, aerospace, space travel, robotics, drones, and / or combinations thereof. The chemical formulas, metals, atoms, and molecular compositions provided herein (the "disclosed formulas") are exemplary only. Those skilled in the art will know that variations on the disclosed formulas can offer tradeoffs to the disclosed solid separator 131 for solid-state lithium ion batteries and can be substituted to achieve similar benefits as the disclosed solid separator 131 for solid-state lithium ion batteries.Additionally, it is contemplated that various considerations may be taken into account with respect to battery manufacturing due to variations in materials and manufacturing techniques, including, but not limited to, polymers, alloys, metals, assemblies, tabs, welding, atmospheric compositions, etc., and combinations thereof. Additionally, while the inventors have contemplated various methods of manufacturing and assembling batteries to achieve greater mass storage capacity (energy density) results, provide high operating currents, increase battery durability and life, increase the range over which the battery can reliably operate, provide safer batteries, and achieve more efficient production means, the present disclosure is not limited to the particular components, advantages listed and described herein, and / or manufacturing methods listed herein.

[0047] The above description and drawings include exemplary embodiments. While exemplary embodiments have been described above, those skilled in the art should note that the disclosure herein is illustrative only, and that various other alternatives, adaptations, and modifications may be made within the scope of the present disclosure. The mere listing or numbering of method steps in a certain order does not constitute any limitation on the order of the method steps. Many modifications and other embodiments will come to mind to one skilled in the art to which this disclosure pertains having the benefit of the teachings presented in the foregoing description and associated drawings. Although specific terms are employed herein, they are used in a generic and descriptive sense only, and not for purposes of limitation. Therefore, the present disclosure is not limited to the specific embodiments described herein, but rather is limited only by the scope of the following claims. This technology includes the following components: . [Configuration 1] At least one cathode; at least one anode; and a battery comprising at least one solid separator in contact with said at least one negative electrode and said at least one positive electrode, said solid separator comprising a base polymer, a structural polymer, and a reinforcing additive that combine to form a solid fibrous mat; . [Configuration 2] 10. The battery of claim 1, wherein the at least one solid separator is self-supporting and non-reactive at room temperature. . [Configuration 3] 2. The battery of claim 1, wherein the main polymer comprises at least one spacer monomer and at least one carbonate monomer. . [Configuration 4] The battery according to the above-mentioned configuration 3, wherein the spacer monomer is at least one monomer selected from the group of monomers consisting of butanediol, hexanediol, triacrylate, diacrylate, and monoacrylate. . [Configuration 5] The at least one carbonate monomer is vinylene carbonate, oxirane, glycidyl acrylate, prop-1-ene The battery according to the above-mentioned configuration 3, wherein the monomer is at least one selected from the group consisting of 1,3-sultone, 4-vinyl-1,3-dioxolan-2-one, succinonitrile, polyacrylonitrile, and allyl methyl carbonate. 。 [Configuration 6] 2. The battery of claim 1, wherein the structural polymer and the reinforcing additive combine to form a solid polymer electrolyte composite. 。 [Configuration 7] 2. The battery of claim 1, wherein the structural polymer is a lithium conductive polymer. 。 [Configuration 8] 8. The battery according to claim 7, wherein the lithium conductive polymer contains at least one lithium ion coordination site selected from the group of lithium ion coordination sites selected from the group consisting of etheric oxygen, carbonate oxygen, silicon, nitrogen, phosphorus, and sulfur. 。 [Configuration 9] 8. The battery according to claim 7, wherein the lithium conductive polymer is at least one polymer selected from the group consisting of polydopamine, polyimide, polyphosphazene, and polysulfonate. 。 [Configuration 10] 10. The battery of claim 1, wherein the solid separator has a thickness of less than 20 microns. 。 [Configuration 11] 10. The battery of claim 1, further comprising an interfacial coating between the separator and the at least one negative electrode. 。 [Configuration 12] 10. The battery of claim 1, further comprising an interfacial coating between the at least one solid separator and the at least one positive electrode. 。 [Configuration 13] The battery according to configuration 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. 。 [Configuration 14] 10. The battery of claim 1, wherein the reinforcing additive is present in an amount not exceeding 10% by weight. 。 [Configuration 15] The battery according to configuration 1, wherein the reinforcing additive is at least one additive selected from the group consisting of LATP, LLZO, LSPSCl, LGPS, lithium conductive halides, clothoborates, and nidoborates. 。 [Composition 16] 10. The battery of claim 1, wherein the structural polymer and the reinforcing additive are combined into a fiber mat by electrospinning. 。 [Composition 17] The battery according to configuration 1, wherein the structural polymer and the reinforcing additive are combined by blade casting to form a fiber mat. 。 [Configuration 18] 1. A solid separator for a battery, comprising: a main polymer comprising at least one spacer polymer and at least one carbonate monomer; a structural polymer having at least one lithium coordination site; and A solid separator for batteries comprising an inorganic reinforcing additive, wherein the main polymer, the structural polymer, and the inorganic reinforcing additive are formed on a porous fiber mat and coated with a lithium conductive interface on at least one side. 。 [Configuration 19] At least one anode; At least one cathode; and A battery comprising a solid separator in contact with the at least one anode and the at least one cathode, the solid separator being made of a nonwoven fiber mat containing a lithium conductive polymer and a solid polymer electrolyte composite. 。 [Configuration 20] The battery according to configuration 19, wherein the nonwoven fiber mat is manufactured by electrospinning or blade casting the lithium conductive polymer and solid polymer electrolyte composite. 。 [Explanation of symbols]

[0048] 100 Solid State Battery 111 Solid-state anode 112 Solid electrolyte 113 bottom 120 Metal ion deposits 131 Solid Separator 132 Cathode current collector 312 Cathode 200 Liquid Electrolyte Battery 211 Liquid electrolyte anode 212 Graphite anode active material 232 Liquid electrolyte cathode current collector 233 Anode current collector 300 Battery 311 Anode 312 Cathode 313 Top surface 331 Separator 351 charger 352 Power receiving device 510 Reinforcing additives 520 Main Polymer 530 Structural Polymers

Claims

1. at least one cathode; at least one anode; and at least one separator in contact with the at least one cathode and the at least one anode; The at least one separator comprises: a primary polymer comprising a fibrous polymer derived from the polymerization of at least one carbonate monomer; a structural polymer comprising a fibrous polymer that provides a skeleton of the at least one separator; and Reinforcing additives containing inorganic materials Contains the at least one separator is configured as a fiber mat in which the base polymer, the structural polymer, and the reinforcing additive are combined in a mat-like form; a solid-state lithium-ion battery, wherein the at least one anode and the at least one cathode do not contain a liquid electrolyte.

2. 10. The solid-state lithium ion battery of claim 1, wherein the at least one separator is self-supporting and non-reactive at room temperature.

3. 10. The solid state lithium ion battery of claim 1, wherein the primary polymer comprises repeat units derived from at least one spacer monomer and at least one carbonate monomer.

4. 4. The solid state lithium ion battery of claim 3, wherein the spacer monomer is at least one monomer selected from the group of monomers consisting of butanediol, hexanediol, triacrylate, diacrylate, and monoacrylate.

5. the at least one carbonate monomer comprises at least one monomer selected from the group consisting of vinylene carbonate, 4-vinyl-1,3-dioxolan-2-one, and allyl methyl carbonate; 4. The solid-state lithium ion battery of claim 3, wherein the base polymer optionally includes at least one repeat unit selected from the group consisting of oxirane, glycidyl acrylate, prop-1-ene 1,3-sultone, succinonitrile, and polyacrylonitrile.

6. 10. The solid-state lithium ion battery of claim 1, wherein at least one of said structural polymer and said reinforcing additive is lithium conductive and combines to form a solid electrolyte composite.

7. 10. The solid state lithium ion battery of claim 1 wherein said structural polymer is a lithium conducting polymer.

8. 8. The solid state lithium ion battery of claim 7, wherein said lithium conducting polymer comprises at least one lithium ion coordination site selected from the group of lithium ion coordination sites selected from the group consisting of etheric oxygen, carbonate oxygen, silicon, nitrogen, phosphorus, and sulfur.

9. 8. The solid state lithium ion battery of claim 7, wherein the lithium conducting polymer is at least one polymer selected from the group of polymers consisting of polydopamine, polyimide, polyphosphazene, and polysulfonate.

10. 10. The solid-state lithium ion battery of claim 1, wherein the separator has a porosity of 90% or greater and a thickness of less than 20 microns.

11. 10. The solid state lithium ion battery of claim 1, further comprising an interface coating between said separator and said at least one cathode.

12. 10. The solid state lithium ion battery of claim 1, further comprising an interfacial coating between said at least one separator and said at least one positive electrode.

13. 10. The solid state lithium ion battery of claim 1, wherein said reinforcing additive is present in an amount not exceeding 10% by weight.

14. 10. The solid state lithium ion battery of claim 1, wherein the reinforcing additive is at least one additive selected from the group of additives consisting of LATP, LLZO, LSPSCl, LGPS, lithium conductive halides, closoborates, and nidoborates.

15. 10. The solid state lithium ion battery of claim 1, wherein said reinforcing additive is combined within said structural polymer in a fibrous form to form a composite.

16. 10. The solid state lithium ion battery of claim 1, wherein said structural polymer and said reinforcing additive are combined in a mixture to form said fiber mat.

17. A separator for a solid-state lithium-ion battery that does not contain a liquid electrolyte, comprising: a primary polymer comprising a fibrous polymer derived from the polymerization of at least one spacer polymer and at least one carbonate monomer; a structural polymer comprising a fibrous polymer having at least one lithium coordination site; and an inorganic reinforcing additive comprising an inorganic material; wherein the primary polymer, the structural polymer, and the inorganic reinforcing additive are combined in a mat form to form a fiber mat, and the fiber mat is coated on at least one side with a lithium conductive interfacial coating.

18. at least one anode; at least one cathode; and a separator in contact with the at least one anode and the at least one cathode; the separator comprises a nonwoven fibrous mat containing a lithium conductive polymer and a solid electrolyte composite, the solid electrolyte composite comprising a fibrous polymer derived from the polymerization of at least one carbonate monomer; the at least one anode and the at least one cathode do not contain a liquid electrolyte; Solid-state lithium-ion battery.

19. 20. The solid state lithium ion battery of claim 18, wherein said nonwoven fiber mat comprises said lithium conductive polymer and solid polymer electrolyte in a composite or mixture.

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