High-energy-density lithium metal-based anodes for solid-state lithium-ion batteries

Abstract

A lithium-based solid-state anode assembly for use in a lithium-ion battery. The anode is formed from an open-pore fibrous ceramic or polymer framework and a lithium-affine active surface material. The open space within the fibrous framework and a lithium-affine coating deposited on the surface of the fibrous framework allow free transport of solid-state lithium ions within the anode. In the solid state, the lithium battery can achieve higher capacity per unit weight, faster charging, and greater durability against harsh handling and temperature. A method for producing a solid-state lithium battery having such an anode is also provided.

Description

[Technical Field]

[0001] The present disclosure relates to chemical devices, i.e., electrical current generating devices. More specifically, the present disclosure relates to the manufacture of battery components with certain improvements to the manufacture of the negative electrode (anode) to improve overall battery performance, safety, and reliability. [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 conventional battery technologies, lithium-ion batteries offer faster charging, greater capacity, and higher power density, enabling improved performance in smaller, lighter packages. There are many reasons why lithium has become a preferred element in battery technology, but the most important reason has to do with its elemental structure. Lithium is highly reactive, easily losing its outermost electrons, allowing current to flow easily through the battery. Lithium is also the lightest metal, much lighter than other metals commonly used in batteries (e.g., lead). This property is important for small items like cell 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 minimize the form factor of electronic devices while simultaneously increasing their capabilities. Smartphones, smartwatches, wearable devices, and other modern, premium electronics simply would not be possible without some of the advances in lithium-ion batteries seen in recent decades.

[0003] Conventional lithium-ion batteries use a liquid electrolyte. The liquid electrolyte in a liquid electrolyte lithium-ion battery is used to regulate the current during charging and discharging. Current "flows" through the liquid electrolyte between the negative and positive electrodes, allowing battery users to store and use electrical energy in the battery. More specifically, lithium ions move through the electrolyte from the negative electrode (anode) to the positive electrode (cathode) during discharge and back during charging. These lithium-ion batteries typically use an intercalated lithium compound as the positive electrode material and graphite as the negative electrode material. Graphite, in its fully lithiated state (LiC6), has a maximum capacity of 372 mAh / g. Summary of the Invention [Problem to be solved by the invention]

[0004] Liquid lithium-ion batteries have high energy density, no memory effect, and low self-discharge, but they can pose safety concerns due to their flammable electrolyte. If these batteries are damaged and exposed to air or not charged properly, they can cause explosions and fires. Recalls due to the fire hazard of removable lithium-ion batteries are common and costly, and some portable electronics manufacturers have even been forced to recall expensive electronics that do not use removable batteries due to lithium-ion fires. This issue has become a growing concern with the incorporation of liquid lithium-ion batteries into electric vehicles (EVs). Liquid lithium-ion batteries in EVs are prone to ignition when exposed to moisture in the air during or immediately after an accident, thereby posing a significant safety risk. This safety issue is becoming increasingly important to address as electric vehicles become increasingly commercially viable and more widely adopted.

[0005] To address these concerns about liquid lithium-ion batteries, much of the research and development effort has focused on developing batteries with liquid-free anodes. Lithium has a maximum capacity of 3600 mAh / g in the solid state, roughly 10 times that of LiC6. However, lithium metal is highly reactive and deposits very unevenly even in the solid state. Liquid electrolyte lithium-ion batteries also typically have a low critical current (0.5 mA / cm). 2 Above plating rates considered to be 0.1 mA / cm, lithium can nucleate and form dendritic or moss-like structures rather than smooth or flat deposits. This is often the cause of swelling, expansion, and even rupture in liquid lithium-ion batteries. In conventional solid lithium foil anode batteries, this current rate is even lower (0.1 mA / cm). 2 ). Therefore, just as many improvements in liquid electrolyte lithium-ion batteries have reduced the likelihood of dendrite or moss formation, it is even more important to promote prevention of this phenomenon when producing solid-state lithium-ion anodes. Batteries with greater energy storage capacity would be advantageous at the same range of charge and discharge rates that consumers and manufacturers expect from modern liquid lithium-ion batteries.

[0006] It is therefore apparent that there is a recognized but unmet need for improvements to achieve high energy density lithium metal-based anodes for solid-state lithium-ion batteries. The present disclosure is designed to address this need through various improvements to the components and internal structure, including the anodes disclosed herein, while addressing at least some aspects of the problems discussed above. [Means for solving the problem]

[0007] Briefly, in possible preferred embodiments, the present disclosure overcomes the aforementioned shortcomings and fulfills the recognized need for lithium-ion negative electrodes with solid electrolytes (i.e., solid-state lithium-ion negative electrodes) by introducing various improvements to the manufacturing, construction, and design of batteries to accommodate such negative electrodes. These generally include, but are not limited to, lithium-ion conductors, electronic conductors, mixed ionic / electronic conductors, lithiophilic coatings, current collectors, and improved welds, individually or in combination. By considering solid-state lithium-ion negative electrodes, 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. Furthermore, these improvements, alone and / or in combination, help reduce the potential for hazards such as fires resulting from swelling, expansion, or breakage of lithium-ion batteries. These improvements, alone and / or in combination, can provide these benefits without reducing charging rates and power delivery to devices.

[0008] One aspect of a high energy density lithium metal-based negative electrode for a solid-state lithium-ion battery can be a lithium-ion conductor. Lithium-ion conductors can be produced in a variety of forms, each with corresponding advantages and tradeoffs. These variations in form can be better understood as separate embodiments of the lithium-ion conductor.

[0009] In a first possible preferred embodiment, the lithium ion conductor may be comprised of a ceramic framework or skeleton. The ceramic framework or skeleton can be used to support lithium metal, a lithium ion conductor. The lithium metal can provide electronic conductivity, while the solid ceramic framework / skeleton can provide spatial support and lithium ion conductivity. One means for combining and / or functionally coupling the lithium metal to the ceramic framework / skeleton can be by melt infusion of the lithium metal into a processed ceramic framework. Initially, only a small amount of lithium metal can be infused into the precursor cell assembly. In such cases, all of the reversible lithium that provides the cell capacity can instead be provided by the cathode in the final assembly. This can occur through high voltage insert cathodes such as lithium ferrophosphate (LFP), lithium cobalt oxide (LCO), nickel / manganese / cobalt (NMC), and / or combinations of these various cathodes. The large surface area of ​​the ceramic scaffold can enhance the operation rate (lithium deposition / stripping) of solid-state batteries compared to flat lithium foils. From an energy density perspective, a key requirement for the ceramic scaffold may be the use of a low density ceramic. An exemplary low density, lightweight ceramic proposed is Li 1+x Al x Ti 2-x P3O 12(LATP). This embodiment of a lithium-ion conductor with a ceramic framework / skeleton may have additional components, manufacturing methods, and further variations with various advantages and tradeoffs. These may include the selection of active materials and the type of functional material processing. These distinctions will become more apparent to those skilled in the art from the following brief description of the drawings, detailed description of illustrative embodiments thereof, and claims, when read in light of the accompanying drawings or figures.

[0010] In a second possible preferred embodiment of the lithium conductor of the disclosed high-energy-density lithium metal-based anode for solid-state lithium-ion batteries, a polymer framework or skeleton is preferred. A polymer framework, which is a lithium conductor of a high-energy-density lithium metal-based anode for solid-state lithium-ion batteries, can offer the additional advantage of being flexible. A ceramic framework can be described as rigid. The requirements for a polymer framework / skeleton include (a) a melting point higher than that of lithium metal (180°C), (b) high lithium ion conductivity, and (c) the incorporation of a lithium conductive material into the structure (e.g., a corresponding lithium salt (e.g., lithium bis(trifluoromethanesulfonyl)imide, LiCFNOS:LiTFSI) or other conductive polymers with ceramic particles embedded in and / or on the surface of the polymer). This embodiment of a lithium-ion conductor with a polymer framework / skeleton may have additional components, manufacturing methods, and further variations with various advantages and tradeoffs. These may include polyimide, aramid, and fiber mats that may further include a polyimide framework. These distinctions will become more apparent to those skilled in the art from the following brief description of the drawings, detailed description of illustrative embodiments thereof, and claims, when read in light of the accompanying drawings or figures.

[0011] In a third possible preferred embodiment of the lithium conductor aspect of the disclosed high-energy-density lithium metal-based negative electrode for solid-state lithium-ion batteries, a hybrid composite framework or scaffold is preferred. This embodiment of the lithium ion conductor with a hybrid composite framework / scaffold may have components, manufacturing methods, and further variations with various benefits and tradeoffs. These may include fumed silica and G4 (tetraglyme) / LiTFSA, fiber mats that may further include boron nitride / vanadium nitride doping, other nitride doping, etc., and / or combinations thereof. These distinctions will become more clear to those skilled in the art from the following brief description of the drawings, detailed description of exemplary embodiments thereof, and claims, when read in light of the accompanying drawings or figures.

[0012] Another aspect of high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries is the electronic conductor. In addition to the injected lithium metal, electronically conductive components may be required in the anode to improve electronic conductivity and uniform deposition during charging. These materials may also play an important role in inhibiting lithium dendritic growth. Eutectic mixtures of lithium with other metals can provide softer lithium-based metal anodes with plastic flow properties.

[0013] Yet another aspect of high-energy density lithium metal-based anodes for solid-state lithium-ion batteries may be the incorporation of mixed ionic / electronic conductors (MIECs) into the battery electrode. In combination with the anodes of the present disclosure, MIECs may be a very promising class of materials for solid electrodes. MIECs differ from solid ionic conductors in that they conduct electrons in addition to ions. MEICs may be best suited for electrodes where both electronic and ionic conductivity may be required. MEICs may not be usable as battery separators where only ionic conductivity (and electronic insulation) is required.

[0014] Yet another aspect of high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries may be a lithiophilic coating on either the ceramic and / or polymer framework / skeleton. The lithiophilic coating may be important for the use of ceramic or polymer frameworks. Because ceramic and / or polymer frameworks / skeletons may not have a good interface with lithium metal in their unmodified state, the modification to incorporate a coating with lithiophilic properties may be important for the inclusion of such types of frameworks / skeleton in high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries. The incorporation of a lithiophilic coating on the ceramic and / or polymer framework / skeleton may further help inhibit dendritic growth of lithium during deposition and / or promote smooth deposition. The lithiophilic coating on the ceramic and / or polymer framework / skeleton may expand the range of suitable choices for the ceramic or polymer framework / skeleton to materials that may react with lithium even without the lithiophilic coating. This may prevent certain ceramics and / or polymers from being used with lithium in an otherwise uncoated state. Lithophilic coatings come in a variety of forms, each of which may involve a unique protocol for distributing and adhering the ceramic and / or polymer framework / coating to the surface. High-energy density lithium metal-based anodes can be understood as fiber or polymer mats that have lithophilic properties, either through the lithophilic properties of the materials used to create the lithophilic framework or through the application of lithophilic coating(s). Here, the fiber or polymer fiber mat has one or more cavities through which lithium or other metals can be deposited.

[0015] Yet another aspect of a high-energy-density lithium metal-based anode for solid-state lithium-ion batteries may be a current collector for the anode. The current collector is an electronic conductor that conducts electrons from the anode to the cathode through an external load, providing power to the load device. Traditionally, copper foil has been used for the anode current collector. The use of copper foil provides support for commercially available graphite anodes. High-energy-density lithium metal-based anodes for solid-state lithium-ion batteries may require the development of new types of current collectors that bond well with the impregnated lithium metal-containing ceramic and / or polymer frameworks. These current collectors may be used for the anodes of the present disclosure, carrying electrons through the load during battery charging and operation.

[0016] Yet another aspect of high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries may be novel fusion methods between high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries, their coatings and components, and surrounding battery components. Copper current collectors are typically tab-welded to one another to carry current to bus bars on the outside of the battery cell. As disclosed herein, development of a weld that tabs the current collectors described herein to a ceramic and / or polymer framework / skeleton bearing a lithophilic coating, in combination with solid lithium metal, may further improve or enable the disclosed high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries.

[0017] Various aspects and features of high-energy density lithium metal-based anodes for solid-state lithium-ion batteries, alone or in combination, may provide significant advantages over conventional liquid electrolyte lithium-ion batteries and existing, available, experimental, and / or proposed solid-state lithium-ion batteries. An advantage of high-energy density lithium metal-based anodes for solid-state lithium-ion batteries may be the ability to increase the energy density of the anode beyond that of currently commercially available graphite-based anodes. Another advantage of high-energy density lithium metal-based anodes for solid-state lithium-ion batteries is that they can achieve a current density of 0.1-0.5 mA / cm currently observed for solid-state batteries. 2 10 mA / cm, which is of significant commercial significance for charging batteries in under 30 minutes. 2Another feature of a high-energy-density lithium metal-based anode for solid-state lithium-ion batteries is that it can provide a safe lithium metal anode structure with lithophilic interphases that can result in a high cycle life (e.g., greater than 4000 cycles), which may be commercially important for electric vehicles and other durable articles that require long on-board battery life. Another feature of a high-energy-density lithium metal-based anode for solid-state lithium-ion batteries is that it can operate over a much wider temperature range (e.g., −60°C to 150°C) than currently available commercial graphite-based anodes (−30°C to 60°C). Another feature of a high-energy-density lithium metal-based anode for solid-state lithium-ion batteries is that it can provide a pre-lithiated anode during fabrication. Another feature of a high-energy-density lithium metal-based anode for solid-state lithium-ion batteries is that it can provide a flexible anode. Another feature of a high-energy density lithium metal-based anode for a solid-state lithium-ion battery may be its ability to pass a nail penetration test, which is not possible with commercially available graphite-based anodes. Another feature of a high-energy density lithium metal-based anode for a solid-state lithium-ion battery may be that the anode is flame-retardant, for example, because the high-energy density lithium metal-based anode for a solid-state lithium-ion battery, which is a potentially preferred embodiment, has a high ceramic content and the batteries of the present disclosure are nearly free of flammable components. Another feature of a high-energy density lithium metal-based anode for a solid-state lithium-ion battery may be various scalable manufacturing methods that result in lithium-based anodes that can be mass-produced.

[0018] These and other features of the high energy density lithium metal-based negative electrodes for solid-state lithium-ion batteries will become more apparent to those skilled in the art from the foregoing Summary of the Invention, as well as the following Brief Description of the Drawings, its Illustrative Detailed Description, and the Claims, when read in light of the accompanying drawings or figures.

[0019] High energy density lithium metal-based negative electrodes for solid state lithium-ion batteries will be better understood by reading the detailed description 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. [Brief explanation of the drawings]

[0020] [Figure 1] FIG. 1 is a perspective view of a cross section of a high energy density lithium metal-based negative electrode for a solid-state lithium-ion battery according to one embodiment of the present disclosure. [Figure 2] FIG. 2 is a diagram of the components of a prior art battery. [Figure 3] FIG. 3 is a block diagram of the battery. [Figure 4] FIG. 4 is a flowchart of a method for producing a high energy density lithium metal-based negative electrode according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0021] In describing one embodiment of the present disclosure, specific terminology is used for clarity, as illustrated in FIGS. 1-4. However, it should be understood that the present disclosure is not intended to be limited to the specific terminology so selected, and that each specific element includes 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 one example among other possible examples. It should be noted that the terms battery, cell, anode, cathode, and separator, in their singular and plural forms, are used in connection with the high-energy-density lithium metal-based anode for the solid-state lithium-ion battery of the present disclosure, as well as to describe other batteries, including, but not limited to, lithium-ion batteries with liquid electrolytes. While a single cell of a battery may be 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. A fibrous framework is used consistently throughout this detailed description and can also be understood as a fibrous cell skeleton.

[0022] 1-4 , by way of example and not limitation, an exemplary embodiment of a high-energy density lithium solid-state anode 111 for a solid-state battery 100 is shown. The solid-state lithium-ion battery 100, the liquid electrolyte battery 200, and the battery 300 are sometimes referred to herein simply as batteries. The high-energy density lithium metal-based solid anode 111, the liquid electrolyte anode 211, and the anode 311 are sometimes referred to herein simply as anodes. While variations in structure, design, composition, chemistry, and assembly may refer to the cathode 312 for clarity and consistency across FIGS. 1-4 , any reference to the cathode 312 will simply be the cathode, and other relevant features may be referenced in the discussions related to the solid-state battery 100, the liquid electrolyte battery 200, and the battery 300. The solid separator 131, the porous separator 231, and the solid separator 131 are sometimes referred to herein simply as separators. The solid-state battery 100, the liquid electrolyte battery 200, and the battery 300 can be charged via a charging device 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 into a multi-layer structure consisting of an anode 311, a cathode 312, and a separator 331. Lithium, lithium metal, elemental lithium, and lithium ions may be referred to interchangeably herein, and the present disclosure is not limited to batteries that include lithium metal as their electro-flow element. Other elements include, but are not limited to, zinc, sodium, cobalt, nickel, lead, potassium, other metals, their salts, etc., and / or combinations thereof.

[0023] In one possible preferred embodiment, solid-state battery 100 can include the following components: a solid anode 111 including 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 one embodiment of liquid electrolyte lithium-ion battery 200, liquid electrolyte lithium-ion battery 200 can include the following components: a liquid electrolyte anode 211 including 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 one embodiment of battery 300, battery 300 can include the following components and connections: anode 311; cathode 312; separator 331; charging device 351; and power receiving device 352.

[0024] Referring now more specifically to FIG. 1 , an example of a solid-state battery 100 is shown. Starting toward the top is a solid anode 111, with solid separators 131 both above and below the solid anode 111. The solid anode 111 can be formed from one or more layers of a solid electrolyte 112, each of which can be formed from a fibrous framework. In general, the solid anode 111 can be understood as a cathode or reduction electrode that gives up electrons to an external circuit (see FIG. 3 ) and is oxidized during an electrochemical reaction. The cathode 312 can be understood as an anode or oxidation electrode that gains electrons from an external circuit (see FIG. 3 ) and is reduced during an electrochemical reaction. In this potentially preferred embodiment, the solid anode 111 can include a solid electrolyte 112, which can be understood as a framework of interconnected fibers. Within the solid anode 111, this framework of interconnected fibers can have a variety of properties and can be flexible or rigid. In the case of a ceramic fiber framework, the ceramic can be utilized to provide structure, support for the solid anode 111 and solid-state battery 100, and a surface onto which lithium or other metals can be deposited. Lithium metal in the metal ion precipitates 120 can provide electronic conductivity for the solid-state battery 100, while the solid ceramic framework / skeleton can provide spatial support, a surface layer for the metal ion precipitates 120, and lithium ion conductivity. During charging and discharging of the solid-state battery 100, the metal ion precipitates 120 can increase in size toward the solid separator 131 and decrease in size toward the center of the solid anode 111. One means for bonding, fabricating, and / or operably engaging the metal ion precipitates 120 with the fiber framework comprising the solid electrolyte 112 can be by melt-infusing lithium metal into a processed ceramic framework. Initially, only a small amount of lithium metal may be required to infuse the precursor cell assembly of the solid anode 111.If the solid anode 111 is injected into a precursor cell assembly in small amounts, most or all of the reversible lithium that gives the cell its capacity may instead come from the cathode 312 of the final assembly. Therefore, during the first charge of the solid-state battery 100, and during all subsequent charges, the metal ion deposit 120 may 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 may be detected or observed to grow in size outward toward the solid separator 131 and may even grow to occupy all the space within the fibrous framework of the solid anode 111 along the solid electrolyte 112. Deposition of lithium and / or other metals may also occur with the temporary use of high-voltage insert cathodes, such as lithium ferrophosphate (LFP), lithium cobalt oxide (LCO), nickel / manganese / cobalt (NMC), and / or combinations of these types of cathodes. The higher surface area of ​​the solid electrolyte 112 with a ceramic fiber framework can enable higher operating rates (lithium deposition / dissolution) of the solid-state battery 100 compared to a flat lithium foil. However, a flat lithium foil can also be used as the initial form of the metal ion deposit 120, melt-injected along the center of the solid-state anode 111 within the solid electrolyte 112.

[0025] From the viewpoint of energy density, a key requirement for the ceramic fiber framework of the solid electrolyte 112 may be the use of low density ceramics. Examples of proposed low density lightweight ceramics are Li 1+x Al x Ti 2-x P3O 12In this embodiment of the solid anode 111 having a ceramic-containing solid electrolyte 112, additional components, manufacturing methods, and further variations are possible, including various advantages and tradeoffs. These can include the selection of active materials and types of functional material processing. In a potentially preferred embodiment of the ceramic version of the solid electrolyte 112, a coating material with specific metal-attracting properties to promote smooth and consistent deposition along the internal fiber framework can provide greater benefits. These can include an engineered solid anode 111 along the solid separator 131 with a total thickness of about 80-90 μm, tailored to a total length and width of about 5 cm x 5 cm, an internal fiber framework with a porosity greater than 70%, individual and / or average fiber diameters less than 0.35 μm, individual and / or average fiber lengths greater than 1 mm, and a coating thickness of about 10 nm, and including a coating material made of an oxide, nitride, polymer, or ceramic. Oxide coating materials for the fibers in the solid electrolyte 112 include, by way of example and without limitation, niobium, Al2O3 + ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur oxides, and the like, and / or combinations of these oxides. Nitride coating materials for the fibers in the solid electrolyte 112 include, by way of example and without limitation, nitridingExamples of suitable coating materials include 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, closoborates (CB), lithium phosphorus oxynitride (LiPON), and the like, and / or combinations thereof. By using one or more coatings on the ceramic fiber structure of the solid electrolyte 112, ceramics that do not readily bond to lithium or other metals can be induced to bond to lithium, thereby acting as an electrolyte through which solid metals containing lithium ions can freely move during charge and discharge.

[0026] In a second possible preferred embodiment of the lithium conductor aspect of the solid-state anode 111 for the solid-state battery 100, a polymer (polymer) framework in the solid electrolyte 112 is preferred. Whereas the previous ceramic fiber framework of the solid electrolyte 112 in the solid-state anode 111 could be described as rigid, the polymer framework of the solid electrolyte 112 in the solid-state anode 111 can provide the added advantage of being flexible. This can provide various benefits and tradeoffs at both the level of the individual cells or layers of the solid-state battery 100, but also in the power receiving device 352 in which the solid-state battery 100 is installed. The polymer framework of the solid anode 111 and the materials deposited therein must meet the following requirements: (a) have a melting point equal to or greater than that of lithium metal (180°C), (b) be non-conductive to lithium ions, and (c) be impregnated with a lithium-conducting material into the solid electrolyte 112 structure. For example, other conductive polymers with corresponding lithium salts (e.g., lithium bis(trifluoromethanesulfonyl)imide / LiCFNOS / LiTFSI) or other conductive polymers with ceramic particles embedded within and / or on their surfaces may be used. This embodiment of the solid anode 111 with a polymer framework for 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 anode 111 and solid electrolyte 112, as well as aramid and polyimide frames. Additionally, not all coatings for ceramic fiber frameworks are applicable to polymer frameworks or polymer fiber frameworks, and not all properties and characteristics of ceramic fiber frameworks are directly applicable to polymer frameworks or polymer fiber frameworks, although some can be applied.These can include an engineered solid anode 111 having a solid electrolyte 112 with a total thickness per layer of about 80-90 μm, a total length and width along the solid separator 131 tailored to about 5 cm x 5 cm, an internal fiber framework porosity greater than 70%, individual and / or average fiber diameters less than 0.35 μm, individual and / or average fiber lengths greater than 1 mm, a coating thickness of about 10 nm, and a coating material including oxides, nitrides, polymers, or ceramics. 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 of these oxides. Nitride coating materials for the fibers in the solid electrolyte 112 are, by way of example and not limitation, examples. nitriding Examples of suitable coating materials for the fibers in the solid electrolyte 112 include, by way of example and not limitation, succinonitrile (SCN). Examples of suitable ceramic coating materials for the fibers in the solid electrolyte 112 include, by way of example and not limitation, closoborate (CB), lithium phosphorus oxynitride (LiPON), and / or combinations thereof. The use of one or more coatings on the ceramic fiber structure of the solid electrolyte 112 can promote the binding of lithium to ceramics that may not readily bind to lithium or other metals, thereby allowing the solid metal containing lithium ions to act as an electrolyte through which they can move freely during charge and discharge.

[0027] The initial deposits of lithium contained in potentially preferred embodiments of either the ceramic or polymer fiber framework of the solid anode 111 and solid electrolyte 112 can be important for several reasons. They may initially form in very small, almost insubstantial amounts in the metal ion deposits 120, but can grow in size, weight, and volume to occupy all empty space within the solid anode 111 and solid electrolyte 112. While this can be achieved by a variety of means, a potentially preferred process for initially depositing metal near the center of the solid anode 111 and onto the surface of the solid electrolyte 112 and its fibers can be by melt pouring of lithium foil.

[0028] Furthermore, the fabrication of the fibers themselves, whether ceramic or polymeric, can provide various important improvements to the structure, formation, and overall properties of the solid electrolyte 112, solid anode 111, and solid-state battery 100. While these techniques may be largely unknown in the battery technology industry, they may have important applications in materials science and the nonwoven materials industry. One such process can involve a sol-gel process, which preferably occurs prior to the deposition of the metal ion precipitate 120. This chemical procedure can form a "sol" (colloidal solution), which can then gradually evolve toward the formation of a gel-like two-phase system containing both liquid and solid phases, with morphologies ranging from discrete particles to a continuous polymer network. In the case of colloids, the particle volume fraction can be very low, so a significant amount of fluid may need to be removed first to realize gel-like properties. One means of removing such fluid can be simply to allow time for settling to occur, followed by pouring off the remaining fluid. Centrifugation can also be used to accelerate the phase separation process. A drying process is required to remove the remaining liquid (solvent) phase, which can result in significant shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the distribution of voids in the gel. The final microstructure of the final component can be strongly influenced by the changes imposed on the structural template during this processing stage. After final sintering, densification, and grain growth, a heat treatment or calcination process is often required to promote further polycondensation and improve mechanical properties and structural stability. One distinct advantage of using this method, as opposed to 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 the desired shape (e.g., to obtain monolithic ceramics, glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g., microspheres, nanospheres).This technique, in combination with electrospinning, is known to create a paper-like material with open pores that are highly suitable for the deposition of metals, i.e., lithium ions. Additional processes that can further enhance this space-filling and open pore properties of the solid electrolyte 112 using various compositions of the disclosed ceramics and polymers include co-precipitation, evaporation and self-assembly, and the use of nanoparticles.

[0029] In either the ceramic or polymer embodiment of the solid electrolyte 112, the material comprising the open-pore fibrous structure or the lithiophilic coating may be considered the active material comprising the solid anode 111. In other words, the active material of the solid anode 111 may be the solid electrolyte 112, which is a solid active material through which lithium ions migrate and concentrate into metal ion precipitates 120. Any active material manufactured to create the solid anode 111 can be processed into a functional material that possesses these properties and functions as the solid electrolyte 112 of the solid-state battery 100. The first step in this processing process may be the synthesis of a fiber mat containing materials such as LATP, closoborate, and sulfide ceramics. The sol-gel or other process step to form the open-pore structure of the solid electrolyte 112 may be improved by reducing the calcination temperature required to effect aliovalent substitution. Other improvements can include maximizing density by using flux additives (e.g., Li2O, MgO, ZnO, Li3PO4, Li3BO3, BO3, 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, active materials from the precursor solid electrolyte 112 assembly may be required to obtain robust and functional laminates, sheets, or mats for use as the solid anode 111. Slurry additives may be added to process the green laminates during rapid sintering. These slurry additives can include, but are not limited to, resins, oils, and dispersants (e.g., PAA, glucose, PVP, ethylene glycol, oleic acid, ultrasonic horns, etc., and / or combinations thereof). Sintering of green materials using conventional techniques known to those skilled in the art can be a lengthy process (>10 hours) and may need to be carried out at high temperatures (>1250° C.) These conventional requirements can result in high operating costs, as well as difficulties in scaling up and undesirable loss of lithium due to evaporation during sintering.Lithium loss at these times and temperatures may need to be addressed by using extra lithium salts during synthesis, which only further increases costs. Instead, a method that allows for scalable application in an open atmosphere and prevents lithium loss or consumption should be used. The resulting sintered green laminate must have voids for post-sintering melt infusion of lithium metal, which can be performed at room temperature. Alternatively, voids can be constructed by using sacrificial plastic / carbon beads or by electrospinning a fiber mat, as described above. The resulting solid electrolyte 112 can then be suitable for lithium deposition along with the metal ion precipitate 120.

[0030] Alternative means for promoting these properties in the solid electrolyte 112 and thereby creating an optimal solid anode 111 include, but are not limited to, reactive sintering of the starting materials, sintering in an electric field, microwave sintering, SPS or spark plasma, low-temperature 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 produced using sacrificial (pore-forming) beads or by developing ceramic fiber mats via electrospinning. Pore-forming beads are various plastics or carbons with low vaporization temperatures that can be removed and / or decomposed, leaving openings in the fiber mat. Other contemplated means, particularly applicable to polymer fiber specifications for the solid electrolyte 112, include the use of polymers with the melting point of lithium metal (180°C). However, because these polymers typically do not conduct lithium ions, their structure can serve a structural role, allowing additional lithium-conducting materials, such as other conductive polymers (with corresponding lithium salts, such as LiTFSI) or ceramic particles, to be infiltrated into their structure. For example, by way of example and not limitation, a fiber mat including polyimide (with a melting point of 450°C) can be used to infiltrate with molten lithium and act as a coating. Further examples include aramid, polyimide frames. Yet another example that provides a suitable structure for the solid electrolyte 112 can be a hybrid composite structure that has properties of both polymer and ceramic fibers. The hybrid composite fiber mat can include fumed silica and G4 / LiTFSA doped with boron / vanadium (or other nitrides) on the surface.

[0031] Even more important to the surface structure and composition of the solid electrolyte 112 may be coating alternatives that, alone or in combination, can provide additional benefits for the deposition, mobility, and smooth deposition of the metal ion deposit 120. These can include CVD / PVD / PECVD and / or ALD deposition in combination with AZO coatings, 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 an integral part of the solid electrolyte 112, which can be developed using sulfur-based solution coating methods, for example, using solutions of polysulfide, dissolved sulfur ZnO-doped argyrodite, Li6PS5Br, Li2S3, or Li3S4 dissolved in DEGDME. Polymer coatings can additionally be employed as surface coatings for the solid electrolyte 112, which can include SN / FECs containing additives and salts (e.g., CsPF, CsTFSI, LiNO, LiF, CuF), elastomers such as SHP, and adhesives such as polydopamine and / or polysiloxane. These various coatings for the solid electrolyte 112 can provide various advantages, including reducing dendritic growth of lithium in the metal ion deposit 120 and during deposition on the solid electrolyte 112, expanding the range of solid electrolyte 112 compositions available for various applications, and preventing reactions between lithium or other metals and various highly useful materials for the construction of the solid anode 111.

[0032] Alternatively, it is contemplated herein that the metal ion deposit 120 may be replaced by an anode current collector disposed in the solid anode 111 within the solid electrolyte 112. These may include foils or coatings onto which metals, particularly lithium, may be deposited. Examples of materials for the anode current collector disposed in the solid anode 111 within the solid electrolyte 112 may include, but are not limited to, vanadium nitride, lithium-aluminum alloys, liquid metals including gallium, indium, and tin, and / or combinations thereof.

[0033] 2, there is shown an example of a cross-sectional view of a cell of a liquid electrolyte lithium-ion battery 200. Generally, a conventional lithium-ion battery such as liquid electrolyte lithium-ion 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 variations of lithium-ion batteries with liquid electrolytes can achieve capacities of 275 Wh / kg and are characterized by the ability to be recharged, but suffer from serious drawbacks, as discussed in the Background section above.

[0034] If sufficient open space is achieved while maintaining the structure, smooth deposition of lithium, and other considerations described herein, the solid-state battery 100 can 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 lithium-ion battery 200 can be compared to the solid-state battery 100 of the present disclosure, which in various forms and combinations achieves over 635 Wh / kg.

[0035] 3 , there is shown a simplified block diagram of a battery 300 having an anode 311, a cathode 312, a separator 331, a charging device 351, and a power receiving device 352. When the cathode 312 is in conductive contact with the charging device 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, and power is supplied (powered) to the charging device 351. Charging and powering each occur via any form of known electrochemical process between the anode 311 and the cathode 312. Various features, components, manufacturing methods, and improvements of the solid-state anode 111 of the solid-state battery 100, as well as the components and features of the battery 300, may be required to successfully manufacture and use the solid-state battery 100. Additionally, various improvements to the components of battery 300, as known and developed in the art of battery manufacturing, including the fabrication of solid-state battery 100, may further increase the benefits described herein of solid-state anode 111. Simply substituting solid-state anode 111 for anode 311 may not be sufficient, and one skilled in the art of battery design and manufacturing can implement and adapt features of solid-state anode 111 to battery 300 to take full advantage of the disclosure herein.

[0036] 4, a flowchart of an exemplary method for manufacturing a solid-state anode 111 for a solid-state battery 100 is shown. Beginning in a first method step 401, a fibrous framework is formed into the active material, the solid-state anode 111. Optionally, in a second (optional) step 402, additional layers of the fibrous framework may be assembled to form the solid-state anode 111, and in a third (optional) step 403, the layers of the fibrous framework may be fused together. In a fourth method step 404, a lithophilic coating may be applied to the solid-state anode 111. In a fifth method step 405, a lithium precipitate may be infused into the solid-state anode 111 to form a metal ion precipitate 120. To form the solid-state battery 100, in a sixth method step 406, the solid anode 111, the solid separator 131, and the solid cathode 312 can be placed in contact with one another, and then a tab weld can be used to connect the solid anode 111 and the solid cathode 312. The steps of the disclosed method of FIG. 4 may be reordered, repeated, and / or rearranged as desired by one skilled in the art to achieve the intended effect.

[0037] With respect to the above description, it should be understood that optimal dimensional relationships are intended to be encompassed by the present disclosure, including variations in size, material, shape, form, location, function and mode of operation, assembly, anode / cathode / battery container type, connection type, and use. It is contemplated that the high-energy-density lithium metal-based anode, i.e., solid anode 111, for a solid-state lithium-ion battery (solid-state battery 100), and the various parts and components described herein, may include various overall sizes and corresponding sizes of the various parts, including, but not limited to, the solid anode 111, solid electrolyte 112, metal ion precipitate 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 herein of the high-energy-density lithium metal-based solid anode 111 for solid-state battery 100 references advantages for electric vehicles and other electronic devices, the present invention is not so limited. The high-energy density lithium metal-based anode for the disclosed solid-state lithium-ion battery may have applications for powering other vehicles, computers, businesses, homes, industrial facilities, consumer and portable electronic devices, hospitals, factories, warehouses, government facilities, data centers, emergency backup, aerospace, space travel, robots, drones, etc., and / or combinations thereof. The chemical formulas, metals, atoms, and molecular compositions ("disclosed formulas") provided herein are exemplary only. One skilled in the art will appreciate that variations on the disclosed formulas provide tradeoffs for the high-energy density lithium metal-based solid-state anode 111 for the disclosed solid-state battery 100 and can be substituted to achieve similar benefits as the high-energy density lithium metal-based anode for the disclosed solid-state lithium-ion battery. Furthermore, it is contemplated that various considerations may be taken into account with respect to battery fabrication due to variations in materials and manufacturing techniques, including, but not limited to, polymers, alloys, metals, assembly, tabbing, welding, atmosphere composition, etc., and combinations thereof.Nonetheless, while the inventors have contemplated various methods of manufacturing and assembling batteries to achieve the results of greater electrical storage capacity per unit mass (energy density), providing high operating currents, increasing the durability and lifespan of the battery, extending the range over which the battery can reliably operate, providing safer batteries, and more efficient manufacturing means, this disclosure is not limited to the specific components, benefits described herein, and / or manufacturing methods described herein.

[0038] The foregoing description and drawings constitute exemplary embodiments. While exemplary embodiments have been described in this manner, those skilled in the art should note that the disclosure herein is illustrative only, and that various other alternatives, applications, and modifications may be made within the scope of the disclosure. The mere listing or numbering of the steps of a method in a certain order does not constitute any limitation on the order of the steps of the method. Numerous modifications and other embodiments will occur to those skilled in the art to which this disclosure pertains having the benefit of the teachings presented in the foregoing description and the associated drawings. Although specific terms may be used herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Therefore, the disclosure is not limited to the specific embodiments illustrated herein, but rather is limited only by the scope of the following claims. The present disclosure encompasses the following configurations: . [Configuration 1] at least one positive electrode having a current collector; at least one negative electrode having a lithophilic fibrous framework; at least one separator in contact with the at least one positive electrode and the at least one negative electrode; a melt-infused lithium foil disposed within the fiber framework; Equipped with the fiber framework, together with the melt-injected lithium foil, forms a solid electrolyte capable of receiving a lithium metal deposit. . [Configuration 2] 10. The battery of claim 1, wherein the lithophilic fiber framework comprises a ceramic fiber mat. . [Configuration 3] 10. The battery of claim 1, wherein the melt-injected lithium foil acts as a current collector in the negative electrode. . [Configuration 4] 10. The battery of claim 1, wherein the lithophilic fibrous framework comprises a polymer mat. . [Configuration 5] 5. The battery of claim 4, wherein the polymer mat is formed by electrospinning. 。 [Configuration 6] 10. The battery of claim 1, wherein the at least one separator is solid. 。 [Configuration 7] 2. The battery of claim 1, wherein the lithophilic fibrous framework further comprises a fibrous material having a lithophilic surface coating deposited thereon. 。 [Configuration 8] said lithiophilic surface coating being at least one coating from a group of coatings; The coating family consists of oxides, nitrides, polymers, and ceramics; The battery according to configuration 7. 。 [Configuration 9] the oxide is at least one oxide from the oxide group, The oxide group includes niobium oxide, Al 2 O 3 +ZnO (AZO), aluminum oxide, indium oxide, zinc oxide, bismuth oxide, magnesium oxide, silicon oxide, gold oxide, iodine oxide, and sulfur oxide. The battery according to configuration 8. 。 [Configuration 10] 8. The battery of claim 7, wherein at least 70% by volume of the lithophilic fibrous framework comprises open pores capable of accepting solid lithium metal derived from lithium ions. 。 [Configuration 11] the lithophilic fibrous framework is formed from at least one material from a group of materials; The group of materials consists of ceramic fibers and polymer fibers. The battery according to configuration 1. 。 [Configuration 12] the at least one material comprises fibers; The fiber group is having a diameter of less than 0.5 μm, a length of greater than 1 mm, and a lithiophilic coating thickness of about 10 nm; arranged to achieve a porosity of greater than 70%, a mat thickness of about 86 μm, and a separator contact area of ​​about 5 cm x 5 cm; The battery according to aspect 11. 。 [Configuration 13] the battery is a lithium ion solid-state battery; the at least one negative electrode and the at least one positive electrode do not contain a liquid electrolyte; The battery according to configuration 1. 。 [Configuration 14] 10. The battery of claim 1, wherein the lithophilic fibrous framework is solid. 。 [Configuration 15] a conductive fiber framework; an active material deposited on the conductive framework, the active material having a lithophilicity capable of accepting 30% by weight of solid lithium metal; Including, anode 。 [Configuration 16] at least one negative electrode of embodiment 1; at least one positive electrode; at least one solid separator in contact with the negative electrode of at least one configuration 1 and the at least one positive electrode; and equipped with a battery . [Configuration 17] 17. The battery of claim 16, wherein the negative electrode further comprises a melt-injected lithium foil disposed in the active material. . [Configuration 18] 18. The battery of claim 17, wherein the active material is a ceramic fiber framework. . [Configuration 19] 18. The battery of claim 17, wherein the active material is a polymer fiber framework. . [Configuration 20] the active material is at least one active material from a group of active materials, the active material group comprises a ceramic fiber framework and a polymer fiber framework; each of the active materials has a lithiophilic coating; The battery according to aspect 17. . [Explanation of symbols]

[0039] 100... solid-state battery, 111... solid negative electrode, 112... solid electrolyte, 120... metal ion precipitate, 131... solid separator, 132... positive electrode current collector, 200... liquid electrolyte battery, 211... liquid electrolyte negative electrode, 212... graphite negative electrode active material, 231... porous separator, 232... liquid electrolyte positive electrode current collector, 233... negative electrode current collector, 300... battery, 311... negative electrode, 312... positive electrode, 331... separator, 351... charging device, 352... power receiving device

Claims

1. at least one positive electrode; A lithium affinity ceramic fiber framework comprising a plurality of lithium affinity ceramic fibers and a plurality of interfiber voids formed between the plurality of lithium affinity ceramic fibers, wherein the lithium affinity ceramic fiber framework has lithium ion conductivity that allows a plurality of lithium ions to conduct along the plurality of lithium affinity ceramic fibers, and the at least one negative electrode comprising the lithium affinity ceramic fiber framework having a lithium affinity ceramic fiber framework comprising a plurality of lithium affinity ceramic fibers, at least one separator in contact with the at least one positive electrode and the at least one negative electrode; A molten-injected lithium foil comprising a molten-injected lithium foil in which at least a portion is disposed on the lithium affinity ceramic fiber framework within the interfiber gaps, The lithium affinity ceramic fiber framework is configured to cooperate with the molten-injected lithium foil to form a current collector that can accept additional lithium metal precipitates into the interfiber voids through the electrochemical reduction of the plurality of lithium ions. A solid-state lithium-ion battery that does not contain a liquid electrolyte.

2. 10. The solid-state lithium-ion battery of claim 1, wherein the lithophilic ceramic fiber framework comprises a ceramic fiber mat.

3. 10. The solid-state lithium ion battery of claim 1, wherein the melt-injected lithium foil acts as a current collector in the negative electrode.

4. 10. The solid-state lithium ion battery of claim 1, wherein the negative electrode comprises a second current collector disposed within the negative electrode.

5. The solid lithium-ion battery according to claim 4, wherein the second current collector comprises at least one selected from the group consisting of vanadium nitride, lithium aluminum alloy, gallium, indium, and tin.

6. 10. The solid-state lithium ion battery of claim 1, wherein the at least one separator is a solid.

7. The lithium affinity ceramic fiber framework comprises a fiber material having a lithium affinity surface coating deposited thereon, the solid lithium-ion battery according to claim 1.

8. said lithophilic surface coating being at least one coating from a group of coatings; 8. The solid state lithium ion battery of claim 7, wherein the coatings consist of oxides, nitrides, polymers, and ceramics.

9. said oxide being at least one oxide from the group of oxides, The oxide group includes niobium oxide, Al 2 O 3 + ZnO (AZO), aluminum oxide, indium oxide, zinc oxide, bismuth oxide, magnesium oxide, silicon oxide, gold oxide, iodine oxide, and sulfur oxide; said nitride being at least one nitride from the group of nitrides; 9. The solid state lithium ion battery of claim 8, wherein the nitride group consists of boron nitride and vanadium nitride.

10. The solid lithium-ion battery according to claim 7, wherein at least 70 volume percent of the lithium affinity ceramic fiber framework includes openings capable of receiving solid lithium metal precipitates derived from lithium ions.

11. the lithiophilic ceramic fiber framework is formed from at least one material from a group of materials; 10. The solid-state lithium ion battery of claim 1, wherein the group of materials consists of ceramic fibers and polymer fibers.

12. the at least one material comprises fibers; The fiber group is having a diameter of less than 0.5 μm, a length of greater than 1 mm, and a lithophilic coating; 12. The solid state lithium ion battery of claim 11 arranged to achieve a porosity of the fiber mat of greater than 70%.

13. 10. The solid-state lithium-ion battery of claim 1, wherein the lithiophilic ceramic fiber framework is a solid.

14. A negative electrode for a solid-state lithium-ion battery, comprising: A conductive fiber framework having a plurality of conductive fibers and a plurality of interfiber gaps formed between the plurality of conductive fibers, wherein the conductive fiber framework has lithium ion conductivity that allows a plurality of lithium ions to conduct along the plurality of conductive fibers, A lithium affinity element comprising at least a portion of which is deposited on the conductive fiber framework within the interfiber gaps, and which has a lithium affinity capable of receiving solid lithium metal, Contains no liquid electrolyte The conductive fiber framework is configured to cooperate with the lithium affinity element to form a current collector that can accept additional lithium metal precipitates in the interfiber voids through the electrochemical reduction of the plurality of lithium ions, thereby forming a negative electrode.

15. At least one negative electrode according to claim 1; at least one positive electrode; A solid lithium-ion battery comprising at least one solid separator in contact with the negative electrode and the at least one positive electrode according to at least one claim 1, and not containing a liquid electrolyte.

16. The solid lithium-ion battery according to claim 15, wherein the negative electrode further comprises a second lithium affinity element and a molten-injected lithium foil disposed within the second lithium affinity element.

17. 17. The solid-state lithium ion battery of claim 16, wherein the second lithophilic element is a ceramic fiber framework.

18. 17. The solid-state lithium ion battery of claim 16, wherein the second lithophilic element is a polymer fiber framework.

19. The solid lithium-ion battery according to claim 16, wherein the second lithium affinity element is at least one selected from the group consisting of ceramic fiber frameworks and polymer fiber frameworks having a lithium affinity coating.

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