High-Energy-Density Lithium-Metal Anodes for Solid-State Lithium-Ion Batteries

Abstract

An assembly to be formed into a lithium-based solid anode for a lithium-ion battery. The anode is formed from a fibrous ceramic or polymer framework with open spaces and an active surface material with lithiophilic properties. The open spaces within the fiber framework and the lithiophilic coating deposited on the fiber framework surface allow solid lithium ions to transport freely within the anode. In the solid state, lithium batteries can achieve higher capacity / weight, charge faster, and be more durable under extreme handling and temperatures. A method for manufacturing a solid-state lithium battery having such an anode.

Description

[0001] BACKGROUND OF THE DISCLOSURE Technical Field

[0002] The present disclosure relates to chemistry, namely, electric current generating devices. More particularly, the present disclosure relates to the fabrication of battery components with certain improvements to the fabrication of the anode to enhance overall battery performance, safety, and reliability. Background Art

[0003] 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, greater capacity, and higher power density, allowing for greater performance in smaller and lighter packages. While there are many reasons why lithium is a favored element in battery technology, the most important one has to do with its elemental structure. Lithium is highly reactive because it readily loses its outermost electrons, allowing current to flow easily through the battery. As the lightest metal, lithium is much lighter than other metals commonly used in batteries, such as lead. This property is important for small objects such as phones, but also for cars, which require many batteries. Finally, lithium ions and electrons easily migrate back to the positive electrode (cathode), allowing for multiple recharging cycles. Innovations in lithium-ion battery technology have helped minimize the form factor of electronic devices while increasing their capacity. Without the advancements in lithium-ion batteries witnessed in recent decades, smartphones, smartwatches, wearable devices, and other modern electronic luxuries would simply not be possible.

[0004] Conventional lithium-ion batteries use liquid electrolytes. The liquid electrolyte solution in liquid electrolyte lithium-ion batteries is used to regulate the flow of current during charging and discharging. Current "flows" through the liquid electrolyte solution between the anode and cathode to allow the battery user to store and then use the battery's stored electrical energy. More specifically, lithium ions move from the negative electrode (anode) through the electrolyte to the positive electrode (cathode) during discharge and back during charging. These lithium-ion batteries typically use intercalated lithium compounds as materials at the cathode and graphite at the anode. Graphite in its fully lithiated state, LiC6, is associated with a maximum capacity of 372 mAh / g.

[0005] Although liquid lithium-ion batteries have high energy density, no memory effect, and low self-discharge, they can pose a safety hazard because they contain flammable electrolytes. If damaged and exposed to air or charged incorrectly, these batteries can cause or even cause explosions and fires. Recalls of removable lithium-ion batteries due to fire hazards are common and expensive, and several portable electronic device manufacturers have even been forced to recall expensive electronic devices without removable batteries due to lithium-ion fires. This issue has become a growing concern due to the incorporation of liquid lithium-ion batteries in electric vehicles (EVs). During and immediately after an accident, the liquid lithium-ion batteries of an EV can easily ignite when exposed to water in the air, causing significant safety issues. As electric vehicles become more commercially viable and more widely adopted, this safety issue becomes increasingly important to address.

[0006] Most of the research and development to address these issues with liquid lithium-ion batteries has focused on developing batteries with liquid-free anodes. Lithium in its solid state has a maximum possible capacity of 3600 mAh / g, or almost ten times that of LiC6. However, lithium metal is also highly reactive in its solid state, and its plates are very heterogeneous. Even in liquid electrolyte lithium-ion batteries, if the deposition rate exceeds what is generally considered a low critical current (0.5 mA / cm 2 ), lithium nucleates and forms dendritic or mossy structures instead of smooth or flat deposits. This is the reason why liquid lithium-ion batteries swell, expand, and even break down many times. In traditional versions of solid lithium foil anode batteries, this current rate is even smaller (0.1mA / cm 2 ). Therefore, just as many advances in liquid electrolyte lithium-ion batteries have reduced the potential for dendritic or mossy formation, advances in preventing such events will be even more important if solid-state lithium-ion anodes are to be produced. If charge and discharge rates were within the same range that consumers and manufacturers expect of modern liquid lithium-ion batteries, then batteries with much greater energy storage capacity would be advantageous.

[0007] Thus, it is apparent that there is a recognized unmet need for improvements in the permissible 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 structures comprising the anodes disclosed herein, while simultaneously addressing at least some aspects of the issues discussed above. Summary of the Invention

[0008] In short, in a potentially preferred embodiment, the present disclosure overcomes the above-mentioned shortcomings and meets the recognized needs for lithium ion anodes with solid electrolytes (i.e., solid-state lithium ion anodes) by introducing various improvements to the manufacture, construction, and design of batteries to accommodate lithium ion anodes with solid electrolytes (i.e., solid-state lithium ion anodes). These generally include, but are not limited to, lithium ion conductors, electron conductors, mixed ion / electron conductors, lithiophilic coatings, one or more current collectors, and improved welding, alone or in combination. By allowing solid-state lithium ion anodes, these improvements have the potential to increase the energy storage capacity of lithium ion batteries from their theoretical maximum in the form of liquid electrolytes to their higher energy density in solid form. In addition, these improvements, alone and / or in combination, help reduce potential hazards, such as fire, caused by expansion, swelling, or damage to lithium ion batteries. These improvements, alone and / or in combination, can allow these benefits without sacrificing charging speed and device power.

[0009] One aspect of high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries can be lithium-ion conductors. Lithium-ion conductors can be manufactured in a variety of forms, each with corresponding benefits and tradeoffs. These variations in form can be better understood as separate, distinct embodiments of lithium-ion conductors.

[0010] In a first potentially preferred embodiment, the lithium ion conductor may be comprised of a ceramic framework. The ceramic framework or skeleton may be used to support the lithium metal of the lithium ion conductor. The lithium metal may provide electronic conductivity, while the solid ceramic framework / skeleton may provide volume support and lithium ion conductivity. One method of combining and / or operably joining the lithium metal to the ceramic framework / skeleton may be by injecting a lithium metal melt into the treated ceramic framework. Initially, only a small amount of lithium metal may need to be injected into the front cell assembly. In such a case where only a small amount is injected into the front cell assembly of the lithium ion conductor, all of the reversible lithium that gives the cell its capacity may come from the cathode in the final assembly. This may occur through high voltage insertion cathodes such as lithium iron phosphate (LFP), lithium cobalt oxide (LCO), nickel / manganese / cobalt (NMC), etc. and / or combinations of various cathodes thereof. The higher surface area of the ceramic skeleton may allow for higher operating rates (lithium plating / stripping) of the solid battery if compared to flat lithium foil. From an energy density perspective, an important requirement for the ceramic skeleton may be to use a low density ceramic. An exemplary low density lightweight ceramic suggested may be Li 1+x Al x Ti 2-x P3O 12(LATP). In this embodiment of the lithium-ion conductor having a ceramic framework / skeleton, additional components, manufacturing methods, and other variations, including various benefits and trade-offs, may exist. These may include the selection of active materials and the type of processing of the functional materials. These differences will become more apparent to those skilled in the art from the following description of the figures, the detailed description of exemplary embodiments thereof, and the claims, when read in light of the accompanying figures or diagrams.

[0011] In a second possible preferred embodiment of the disclosed lithium conductor for a high energy density lithium metal-based anode for a solid-state lithium ion battery, a polymer framework or skeleton may be preferred. The polymer framework / framework for the lithium conductor for a high energy density lithium metal-based anode for a solid-state lithium ion battery can provide the additional benefit of flexibility, where the ceramic framework / skeleton can be described as rigid. The requirements for the polymer framework / skeleton can be (a) having a melting point higher than the melting point of lithium metal (180°C), (b) high conductivity of lithium ions, and (c) infusion of lithium conductive materials into the structure, such as other conductive polymers with corresponding lithium salts (e.g., lithium bis(trifluoromethanesulfonyl)imide / LiC2F6NO4S2 / LiTFSI) or ceramic particles embedded in the polymer and / or on its surface. In this embodiment of the lithium ion conductor with a polymer framework / skeleton, there may be additional components, manufacturing methods, and other variations including various benefits and trade-offs. These may include fiber mats, which may further include polyimide, aromatic polyamide, and a polyimide framework. These distinctions will become more readily apparent to those skilled in the art from the following description of the drawings, detailed description of exemplary embodiments thereof, and claims, when read in light of the accompanying drawings or figures.

[0012] In a third possible preferred embodiment of the disclosed lithium conductor for a high energy density lithium metal based anode for a solid state lithium ion battery, a hybrid composite framework or skeleton may be preferred. In this embodiment of the lithium ion conductor having a hybrid composite framework / skeleton, there may be additional variations in components, manufacturing methods, and including various benefits and tradeoffs. These may include fiber mats, which may further include fumed silica and G4 / LiTFSA, boron nitride / vanadium nitride doping, doping of other nitrides, etc. and / or combinations thereof. These distinctions will become more apparent to those skilled in the art from the following description of the figures, detailed description of exemplary embodiments thereof, and the claims when read in light of the accompanying drawings or figures.

[0013] Another aspect of high-energy-density lithium metal-based anodes for solid-state lithium-ion batteries is electron conductors. In addition to the injected lithium metal, electron-conducting components may be required in the anode to improve electron conductivity and uniform precipitation during charging. These materials can also play a vital role in suppressing the growth of lithium dendrites. Eutectics of lithium and other metals can provide softer lithium-based metal anodes with plastic flow properties.

[0014] Yet another aspect of high energy density lithium metal-based anodes for solid-state lithium-ion batteries may be the introduction of mixed ion / electron conductors (MIECs) at the battery electrodes. Combined with the anodes disclosed herein, MIECs may be a very promising class of solid electrode materials. MIECs differ from solid ion conductors in that, in addition to ions, they also conduct electrons. MEICs may be best suited for electrodes where both electronic and ion conduction may be required. MEICs may not be useful as battery separators where only ionic conductivity (and electronic insulation) may be required.

[0015] Yet another aspect of high energy density lithium metal-based anodes for solid-state lithium-ion batteries can be a lithiophilic coating of ceramic and / or polymer frameworks / skeletons. Lithiophilic coatings can be crucial for the use of ceramic or polymer frameworks. Since ceramic and / or polymer frameworks / skeletons may not have a good interface with lithium metal in their unmodified state, improvements that introduce coatings with lithiophilic properties can be crucial for including these types of frameworks / skeletons in high energy density lithium metal-based anodes for solid-state lithium-ion batteries. Introducing lithiophilic coatings into ceramic and / or polymer frameworks / skeletons can further promote the reduction of lithium dendrite growth during precipitation and / or promote smooth precipitation. Lithiophilic coatings of ceramic and / or polymer frameworks / skeletons can also expand the range of suitable ceramic or polymer frameworks / skeletons to materials that can otherwise react with lithium in the absence of a lithiophilic coating, thereby further preventing certain ceramics and / or polymers from being used with lithium in their uncoated state. Lithiophilic coatings come in a variety of forms, each of which can involve strategies for distributing and adhering themselves to the surface of the ceramic and / or polymer framework / coating. By the lithiophilic properties of the material used to produce the lithiophilic framework, or by adding one or more lithiophilic coatings, the high energy density lithium metal-based anode can be understood as a fiber felt or polymer felt with lithiophilic properties, the fiber felt or polymer fiber felt having one or more cavities through which lithium or other metals can be deposited.

[0016] Yet another aspect of a high energy density lithium metal based anode for a solid state lithium ion battery may be a current collector for the anode. A current collector is an electron conductor that carries electrons from the anode to the cathode through an external load to power the load device. Traditionally, copper foil has been used for the anode current collector. The use of copper foil further supports commercial graphite anodes. In a high energy density lithium metal based anode for a solid state lithium ion battery, it may be desirable to develop a new type of current collector that combines well with a ceramic and / or polymer framework / skeleton with infused lithium metal, which may be the current collector for the anode of the present disclosure to carry electrons through the load during charging and operation of the battery.

[0017] Yet another aspect of high energy density lithium metal-based anodes for solid-state lithium ion batteries can be a novel method of incorporating high energy density lithium metal-based anodes for solid-state lithium ion batteries, their coatings and components, and surrounding battery components. Copper current collectors can typically be tabbed together to carry the electron current to a busbar outside the battery cell. As disclosed herein, the development of welding current collector tabs as described herein to ceramic and / or polymer frameworks / skeletons having a lithiophilic coating and combined with solid lithium metal can further enhance or even enable the high energy density lithium metal-based anodes for solid-state lithium ion batteries of the present disclosure.

[0018] Various aspects and features of a high energy density lithium metal-based anode for a solid-state lithium ion battery may, individually or in combination, provide benefits over both conventional liquid electrolyte lithium ion batteries and existing, available, experimental, and / or proposed solid-state lithium ion batteries. A benefit of a high energy density lithium metal-based anode for a solid-state lithium ion battery may be that it is able to increase the energy density of the anode to a level higher than that of current commercial graphite-based anodes. Another benefit of a high energy density lithium metal-based anode for a solid-state lithium ion battery may be that it is able to provide a higher energy density than the 0.1-0.5 mA / cm currently observed for solid-state batteries. 2 and close to as high as 10mA / cm 2A high operating current, which may be of great commercial significance for charging the battery in less than 30 minutes. Another feature of the high energy density lithium metal-based anode for solid-state lithium-ion batteries may be its ability to provide a safe lithium metal anode structure with a lithiophilic interface, which may lead to a high cycle life (e.g., greater than 4000 cycles), which may also be of commercial significance for electric vehicles and other durable goods that require long-life installed batteries. Another feature of the high energy density lithium metal-based anode for solid-state lithium-ion batteries may be the ability to operate over a much wider temperature range (e.g., -60°C to 150°C) than even currently available commercial graphite-based anodes (-30°C to 60°C). Another feature of the high energy density lithium metal-based anode for solid-state lithium-ion batteries may be the ability to provide a pre-lithiated anode during manufacturing. Another feature of the high energy density lithium metal-based anode for solid-state lithium-ion batteries may be the ability to provide a flexible anode. Another feature of the high energy density lithium metal-based anode for solid-state lithium-ion batteries may be the ability to pass a needle penetration test that commercial graphite-based anodes cannot pass. Another feature of the high energy density lithium metal-based anodes for solid-state lithium ion batteries can be the ability of the anode to resist combustion because, for example, due to the high ceramic content of possible preferred embodiments of the high energy density lithium metal-based anodes for solid-state lithium ion batteries, there will be almost no flammable components in the battery of the present disclosure. Another feature of the high energy density lithium metal-based anodes for solid-state lithium ion batteries can be various scalable processes to produce lithium-based anodes that can be mass-produced.

[0019] These and other features of the high energy density lithium metal-based anode for solid-state lithium ion batteries will become more readily apparent to those skilled in the art from the preceding summary and subsequent description of the drawings, detailed description of exemplary embodiments thereof, and claims, when read in light of the accompanying drawings or figures. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The high energy density lithium metal-based anode for solid-state lithium-ion batteries will be better understood by reading the detailed description with reference to the accompanying drawings, which are not necessarily drawn to scale and in which like reference numerals represent similar structures and refer to like elements throughout, and in which:

[0021] Figure 1 is a cross-sectional perspective view of an exemplary embodiment of a high energy density lithium metal-based anode for a solid-state lithium ion battery of the present disclosure.

[0022] Figure 2 is a diagram of components of a prior art battery.

[0023] Figure 3 This is a block diagram of a battery.

[0024] Figure 4is a flow chart illustrating a method for making a high energy density lithium metal-based anode of the present disclosure.

[0025] It should be noted that the drawings presented are intended for illustration purposes only and therefore they are neither intended nor intended to limit the disclosure to any or all exact details of the construction shown, except as may be considered essential to the claimed disclosure. DETAILED DESCRIPTION

[0026] In describing the present disclosure Figure 1-4 When describing the exemplary embodiments shown in the accompanying drawings, specific terms are used for the sake of clarity. However, the present disclosure is not intended to be limited to the specific terms so selected, and it should be understood that each specific element includes all technical equivalents that operate in a similar manner to achieve similar functions. However, the embodiments of the claims can be embodied in many different forms and should not be interpreted as being limited to the embodiments set forth herein. The examples set forth herein are non-limiting examples and are merely examples of other possible examples. It should be noted that the terms battery, cell, anode, cathode and separator are used in their singular and plural forms as they relate to the high energy density lithium metal-based anodes for solid-state lithium-ion batteries of the present disclosure, as well as for describing other batteries, including but not limited to lithium-ion batteries with liquid electrolytes. Although a single battery cell of a battery may be described herein, those skilled in the art of battery manufacturing will understand that multiple battery cells can be used in the design, construction, manufacture and assembly of the battery, and that multiple batteries can be arranged and / or installed in the finished product. Although fiber frame is used throughout this detailed description, it can also be understood as a fiber battery skeleton.

[0027] Now for reference only as an example and not as a limitation Figure 1-4 , wherein an exemplary embodiment of a high energy density lithium solid state anode 111 for a solid state battery 100 is described. The solid state lithium ion battery 100, the liquid electrolyte battery 200, and the battery 300 may be referred to herein as simply a battery. 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 as simply an anode. Although variations in construction, design, composition, chemistry, and assembly are possible with respect to the cathode 312, Figure 1-4For clarity and consistency, any reference to cathode 312 is simply the cathode, and other related features may be referred to in the description as it relates to solid-state battery 100, liquid electrolyte battery 200, and battery 300. Solid separator 131, porous separator 231, and solid separator 131 may be referred to herein as simply separators. Solid-state battery 100, liquid electrolyte battery 200, and battery 300 may be charged by charger 351 and discharged into device 352. As described herein, solid-state battery 100, liquid electrolyte battery 200, and battery 300 may each have a single cell or may have multiple cells connected and / or assembled in multiple layers of anode 311, cathode 312, and 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 having lithium metal as their current element. Other elements may include, but are not limited to, zinc, sodium, cobalt, nickel, lead, potassium, other metals, salts thereof, and / or combinations thereof.

[0028] In one potentially preferred exemplary embodiment, solid-state battery 100 may include the following components: a solid-state anode 111 having a solid electrolyte 112 and a fiber framework and shown with a metal ion deposit 120, a solid separator 131, and a cathode 312 having a solid cathode current collector 132. In embodiments of liquid electrolyte lithium-ion battery 200, liquid electrolyte lithium-ion 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 embodiments of battery 300, battery 300 may include the following components and connections: anode 311, cathode 312, separator 331, charger 351, and power supply 352.

[0029] Now with more particular reference Figure 1 , in which an example of a solid-state battery 100 is illustrated. Starting from the top is a solid anode 111 with a solid separator 131 above and below the solid anode 111. The solid anode 111 can be formed of one or more layers of a solid electrolyte 112, wherein each layer of the solid electrolyte 112 can be formed of a fiber framework. In general, the solid anode 11 can be understood as releasing electrons to an external circuit (see Figure 3 ) and oxidizes during the electrochemical reaction. The cathode 312 can be understood as a negative electrode or a reduction electrode that takes electrons from an external circuit (see Figure 3) and is reduced during the electrochemical reaction, either as a positive electrode or an oxidizing electrode. In this potentially preferred embodiment, the solid-state anode 111 can be composed of a solid electrolyte 112, which can be understood as a framework of interconnected fibers. The framework interconnected fibers in the solid-state anode 111 can have a variety of properties and can be flexible or rigid. In the case of a ceramic fiber framework, the ceramic can be used to provide structure, support, and a surface on which lithium or other metals can be deposited for the solid-state anode 111 and the solid-state battery 100. The lithium metal at the metal ion deposit 120 can provide electronic conductivity for the solid-state battery 100, while the solid ceramic framework / skeleton can provide volume support, a surface layer for the metal ion deposit 120, and lithium ion conductivity. During charging and discharging of the solid-state battery 100, the size of the metal ion deposit 120 can increase toward the solid separator 131 or shrink toward the center of the solid-state anode 111. One method of combining, manufacturing, and / or operatively joining the metal ion deposit 120 with the fiber framework of the solid electrolyte 112 can be by injecting a lithium metal melt into the treated ceramic framework. Initially, only a small amount of lithium metal may need to be injected into the front cell assembly of the solid-state anode 111. In such cases, where only a small amount is injected into the front cell assembly of the solid-state anode 111, most or even all of the reversible lithium that gives the cell its capacity can come from the cathode 312 in the final assembly. Therefore, during the first charge of the solid-state battery 100 and all subsequent charges, a very small metal ion deposit 120 can be detected or observed at or near the center of the solid-state anode 111. During the charging process of the solid-state battery 100, the metal ion deposit 120 can be detected or observed to increase in size outward toward the solid separator 131, even growing to occupy all space within the fibrous framework of the solid-state anode 111 along the solid electrolyte 112. Deposition of lithium and / or other metals can further occur by temporarily using a high-voltage insertion cathode such as lithium iron phosphate (LFP), lithium cobalt oxide (LCO), nickel / manganese / cobalt (NMC), etc., and / or combinations thereof. The higher surface area of the solid electrolyte 112 with a ceramic fiber framework, compared to a flat lithium foil, can allow for a higher operating rate (lithium precipitation / dissolution) of the solid-state battery 100. However, the flat lithium foil can also be used as an initial form of metal ion deposit 120 and can also be melt-infused into the solid electrolyte 112 along the center of the solid anode 111.

[0030] From the perspective of energy density, an important requirement for the ceramic fiber framework of the solid electrolyte 112 may be to use low density ceramics. An exemplary low density lightweight ceramic suggested may be Li 1+x Al x Ti 2-x P3O 12(LATP). In this embodiment of the solid-state anode 111 having a solid electrolyte 112 comprising a ceramic, there may be additional components, manufacturing methods, and other variations including various benefits and trade-offs. These may include the selection of active materials and functional material processing 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 provide added benefits to promote smooth, consistent precipitation along the internal fiber framework. These may include engineered solid-state anodes 111 having a solid electrolyte 112 to measure a total thickness of approximately 80-90 μm per layer, a total length and width along the solid separator 131 of approximately 5 cm x 5 cm, a porosity percentage of greater than 70% of the internal fiber framework, a single and / or average fiber diameter of less than 0.35 μm, a single and / or average fiber length of greater than 1 mm, a coating thickness of approximately 10 nm, and a coating material comprising an oxide, nitride, polymer, or ceramic. By way of example and not limitation, oxide coating materials for fibers within the solid electrolyte 112 include oxides of niobium, Al2O3+ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur, and / or combinations thereof. By way of example and not limitation, nitride coating materials for fibers within the solid electrolyte 112 include boron, vanadium nitride, and / or combinations thereof. By way of example and not limitation, polymer coating materials for fibers within the solid electrolyte 112 include succinonitrile (SCN). By way of example and not limitation, ceramic coating materials for fibers within the solid electrolyte 112 include closed borates (CB), lithium phosphorus oxynitride (LiPON), and / or combinations thereof. By applying one or more coatings to the ceramic fiber structure of the solid electrolyte 112, ceramics that may not readily bind to lithium or other metals can be encouraged to bind to lithium, thereby acting as an electrolyte over which solid metals including lithium ions can freely move during charging and discharging.

[0031] In a second possible preferred embodiment of the lithium conductor for the solid-state anode 111 of the solid-state battery 100, a polymer framework in the solid electrolyte 112 is preferred. The polymer framework of the solid electrolyte 112 within the solid-state anode 111 can provide the added benefit of flexibility, where previous ceramic fiber frameworks of the solid electrolyte 112 within the solid-state anode 111 can be described as rigid. This can provide various benefits and tradeoffs at the level of individual cells or layers of the solid-state battery 100, and also provide various tradeoffs and benefits for the power supply 352 in which the solid-state battery 100 is installed. Requirements for the polymer framework of the solid-state anode 111 and the materials deposited therein can be (a) a melting point above the melting point of lithium metal (180°C), (b) non-conductivity of lithium ions, and (c) incorporation of lithium-conducting materials into the structure of the solid electrolyte 112, such as other conductive polymers with corresponding lithium salts (e.g., lithium bis(trifluoromethanesulfonyl)imide / LiC2F6NO4S2 / LiTFSI) or ceramic particles embedded in the polymer and / or on its surface. In this embodiment of a solid-state anode 111 with a polymeric framework of a solid electrolyte 112, additional components, manufacturing methods, and other variations with various benefits and tradeoffs are possible. These may include a fiber mat extending throughout the solid-state anode 111 and solid electrolyte 112, which may further include an aramid or polyimide framework. Furthermore, while not all coatings for ceramic fiber frameworks are suitable for polymer or polymer fiber frameworks, and while not all properties and characteristics of ceramic fiber frameworks are directly applicable to polymer or polymer fiber frameworks, some are. These may include engineered solid-state anodes 111 with a solid electrolyte 112 measuring approximately 80-90 μm in total thickness per layer, approximately 5 cm x 5 cm in total length and width along the solid separator 131, a porosity greater than 70% within the fiber framework, 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 approximately 10 nm, and a coating material comprising an oxide, nitride, polymer, or ceramic. By way of example and not limitation, oxide coating materials for fibers within the solid electrolyte 112 include oxides of niobium, Al2O3+ZnO (AZO), aluminum, indium, zinc, bismuth, magnesium, silicon, gold, iodine, and sulfur, and / or combinations thereof. By way of example and not limitation, nitride coating materials for fibers within the solid electrolyte 112 include boron, vanadium nitride, and / or combinations thereof. By way of example and not limitation, polymer coating materials for fibers within the solid electrolyte 112 include succinonitrile (SCN). By way of example and not limitation, ceramic coating materials for fibers within the solid electrolyte 112 include closed borates (CB), lithium phosphorus oxynitride (LiPON), and / or combinations thereof.By using one or more coatings on the ceramic fiber structure of the solid electrolyte 112, ceramics that may not readily bond with lithium or other metals can be encouraged to bond with lithium, thereby acting as an electrolyte over which solid metal including lithium ions can move freely during charging and discharging.

[0032] In potentially preferred embodiments of the ceramic fiber framework or polymer fiber framework included in the solid anode 111 and solid electrolyte 112, initial deposition of lithium can be important for several reasons. These can initially form in very small, almost insignificant amounts at the metal ion deposits 120, but increase in size, weight, and volume, and can even occupy all empty space within the solid anode 111 and solid electrolyte 112. This can be accomplished in a variety of ways, although a potentially preferred process for initially depositing metal near the center of the solid anode 111 on the surface of the solid electrolyte 112 and its fibers can be by melt injection of lithium foil.

[0033] Furthermore, the fabrication of the fibers themselves, whether ceramic or polymeric, can provide a variety of important improvements to the structure, formation, and overall properties of the solid electrolyte 112, solid anode 111, and solid-state battery 100. These techniques may have few or no known applications in the battery technology industry, but may have important applications in the materials science and nonwovens industries. One such process may include a sol-gel process, which may preferably occur prior to the deposition of the metal ion deposit 120. In this chemical procedure, a "sol" (colloidal solution) can form, which then gradually evolves to form a gel-like two-phase system containing both a liquid and a solid phase, with morphologies ranging from discrete particles to a continuous polymer network. In the case of colloids, the volume fraction of the particles can be low, necessitating the initial removal of a large amount of fluid for the gel-like properties to be recognized. One such fluid removal method may be to simply allow time for sedimentation to occur and then discard 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 and can result in significant shrinkage and densification. The rate at which the solvent can be removed is ultimately determined by the porosity distribution within the gel. The final microstructure of the final component is strongly affected by the changes imposed on the structural template during this processing stage. A heat treatment or firing process is usually necessary to promote further polycondensation and improve mechanical properties and structural stability through final sintering, densification and grain growth. In contrast to more traditional processing techniques, one of the obvious advantages of using this method is that densification is usually achieved at much lower temperatures. The precursor sol can be deposited on a substrate to form a film (e.g., by dip coating, spin coating or electrospinning), cast into a suitable container with a desired shape (e.g., to obtain a monolithic ceramic, glass, fiber, film, aerogel) or used to synthesize powders (e.g., microspheres, nanospheres). It is known that this technology, combined with electrospinning, produces a paper-like material with an open cavity that is very suitable for the deposition of metals (i.e., lithium ions). Using various compositions of the disclosed ceramics and polymers, additional processes that can further enhance the space filling and open cavity characteristics of the solid electrolyte 112 can include co-precipitation, evaporation and self-assembly, as well as the use of nanoparticles.

[0034] In the ceramic or polymer embodiment of the solid electrolyte 112, the material having a fiber structure with an open cavity, a fiber structure with a lithium-philic coating can be considered to be an active material, including the solid anode 111. In other words, the active material of the solid anode 111 can be the solid electrolyte 112, which is an active material through which lithium ions migrate and accumulate at the metal ion deposit 120. Any active material manufactured to produce the solid anode 111 can be processed into a functional material having these properties and serving as the solid electrolyte 112 of the solid-state battery 100. The first stage of the process can be a synthetic fiber felt, including substances such as LATP, closed borate and sulfide ceramics. The stage in the sol-gel or other process of forming the open cavity structure of the solid electrolyte 112 can be improved by reducing the firing temperature required to implement aliovalent substitution. Other improvements may 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). In order to achieve functional material processing of the solid electrolyte 112, it may be necessary to pre-assemble the active materials of the solid electrolyte 112 to obtain a strong functional laminate, sheet, or felt for use as the solid 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 the green material using conventional techniques known to those skilled in the art can be a long process (>10 hours) and may require high temperatures (>1250°C). These conventional requirements may require high-cost operations, are difficult to scale up, and result in undesirable loss of lithium due to evaporation during sintering. The loss of lithium at these times and temperatures may need to be countered by using additional lithium salts during synthesis, which only further increases costs. Instead, a method should be substituted that allows for scalable application in an open environment and prevents lithium loss or depletion. The resulting sintered green laminate should contain voids for lithium metal melt injection, which can then occur at room temperature after sintering. As described above, voids can be constructed by using sacrificial plastic / carbon beads or by electrospinning them into fiber mats. The resulting solid electrolyte 112 can then be suitable for depositing lithium along with the metal ion deposit 120.

[0035] Alternative measures to promote these properties in the solid electrolyte 112 to produce an optimal solid anode 111 may include reactive sintering of raw materials, sintering in an electric field, microwave sintering, SPS or spark plasma, cold sintering using solvent evaporation and salt CSP, and rapid sintering using high currents. Alternatively, or in combination with these techniques for developing solid electrolytes 112, porous sheets can be made using sacrificial beads, which are various plastics or carbons with low evaporation temperatures that can be removed and / or destroyed to leave openings in the fiber mat, or ceramic fiber mats can be developed by electrospinning. Other contemplated means for polymer fiber versions of the solid electrolyte 112 that are particularly suitable include using polymers with a lithium metal melting point (180°C). However, these polymers generally do not conduct lithium ions, so they will play a structural role under which additional lithium conducting materials can be injected into the structure, such as other conducting polymers (with corresponding lithium salts, such as LiTFSI) or ceramic particles. For example, by way of example and not limitation, a fiber mat comprising polyimide (having a melting point of 450° C.) can be used to infuse molten lithium and act as a coating. Other examples include aromatic polyamide, polyimide frameworks. Yet another example of providing a suitable formation for the solid electrolyte 112 can be a hybrid composite structure having characteristics of both polymer fibers 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.

[0036] More importantly for the surface structure and composition of the solid electrolyte 112, coating alternatives may be used that can provide additional benefits, alone or in combination, to the deposition, mobility, and smooth precipitation of the metal ion deposit 120. These may include CVD / PVD / PECVD and / or ALD vapor deposition in combination with AZO coatings using I2, Li3N, Li3PO4, LLZO, Li9AlSiO8, Li3OCl, LiI:4CH3OH, or 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 a key component of the solid electrolyte 112, which can be developed using sulfur-based solution coating methods using, for example, solutions of polysulfides dissolved in DEGDME, dissolved sulfur ZnO doped argyrodite Li6PS5Br, Li2S3, or Li3S4. Polymer coatings can also be used as surface coatings for the solid electrolyte 112, which can include SN / FEC with additives and salts (e.g., CsPF6, CsTFSI, LiNO3, LiF, CuF2), elastomers such as SHP, and even glues such as polydopamine and / or polysiloxane. These various coatings of the solid electrolyte 112 can provide a variety of benefits, including reducing dendrite growth of lithium during precipitation at the metal ion deposits 120 and on the solid electrolyte 112, expanding the range of possible choices for solid electrolyte 112 compositions for various applications, and preventing reactions between various very useful materials used to construct the solid anode 111 and lithium or other metals.

[0037] Alternatively, it is contemplated herein that the metal ion deposit 120 may be replaced by an anode current collector in a solid anode 111 disposed within the solid electrolyte 112. These may include foils or coatings on which metal, particularly lithium, may be deposited. Exemplary materials for the anode current collector in the solid anode 111 disposed within the solid electrolyte 112 may include, but are not limited to, vanadium nitride, one or more lithium-aluminum alloys, liquid metals (including gallium, indium, and tin, among others), and / or combinations thereof.

[0038] Now specifically refer to Figure 2 , which illustrates an example of a cross-sectional view of a battery cell of a liquid electrolyte lithium-ion battery 200. Generally, a conventional lithium-ion battery, which is a 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 variants of lithium-ion batteries with liquid electrolytes can achieve a capacity of 275 Wh / kg and are rechargeable, but have serious drawbacks as discussed in the background section above.

[0039] If sufficient open space is achieved while maintaining structure, smooth lithium deposition, and other considerations described herein, the solid-state battery 100 can achieve significantly higher capacities while allowing for additional benefits such as durability, safety, fast charging, and the other benefits described above. For example, the 275Wh / kg capacity of the liquid electrolyte lithium-ion battery 200 can be compared to the solid-state battery 100 of the present disclosure, which has various forms and combinations, reaching over 635Wh / kg.

[0040] Now special reference Figure 3 , which illustrates a simple block diagram of a battery 300 having an anode 311, a cathode 312, a separator 331, a charger 351, and a power supply 352. When cathode 312 is in conductive contact with charger 351, it completes an electrical circuit with anode 311, thereby charging battery 300. Alternatively, when cathode 312 is in conductive contact with power supply 352, it completes an electrical circuit with anode 311 and powers power supply 351. Each of charging and powering occurs through any known electrochemical process between anode 311 and cathode 312. In addition to the various features, components, manufacturing methods, and improvements to the solid-state anode 111 of solid-state battery 100 as described herein, the components and features of battery 300 may be required to fully manufacture and use solid-state battery 100. Furthermore, various improvements to the components of battery 300, as known and developed in the art of battery manufacturing, including the manufacture of solid-state battery 100, may further enhance the benefits of the solid-state anode 111 as described herein. Simply replacing anode 311 with solid-state anode 111 may not be sufficient, and one skilled in the art of battery design and manufacturing may implement and adapt the features of solid-state anode 111 into battery 300 to fully utilize the disclosure herein.

[0041] Now special reference Figure 4 , a flow chart of an exemplary method for manufacturing a solid-state anode 111 for a solid-state battery 100 is illustrated. Starting from a first method step 401, a fiber framework is formed into a solid-state anode 111, which is an active material. Optionally, additional fiber framework layers can be assembled in a second step (optional) 402 to form the solid-state anode 111, and the fiber framework layers can be melted in a third step (optional) 403. In a fourth method step 404, a lithium-philic coating can be applied to the solid-state anode 111. In a fifth method step 405, a lithium deposit can be injected into the solid-state anode 111 to form a metal ion deposit 120. To form the solid-state battery 100, the solid-state anode 111, the solid separator 131 and the solid-state cathode 312 can be placed in contact with each other in a sixth method step 406, and then the solid-state anode 111 and the solid-state cathode 312 can be connected using tab welding. Figure 4The steps of the disclosed methods may be rearranged, repeated, and / or re-ordered as one skilled in the art would wish to achieve the desired results.

[0042] With respect to the above description, then, it should be recognized that optimal dimensional relationships, including variations in size, material, shape, form, position, function and mode of operation, assembly, type anode / cathode / battery container, type of one or more connections, and use are intended to be encompassed by the present disclosure. It is contemplated herein that a high energy density lithium metal-based anode or 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 various parts and various parts, including but not limited to: 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. In practice, during standard operation of the solid-state battery 100, those different parts and components of the solid-state battery 100 may vary in size, shape, etc. The description herein of the high energy density lithium metal-based solid-state anode 111 for the solid-state battery 100 mentions benefits to electric vehicles and other electronic devices, but the invention is not limited thereto. The high energy density lithium metal-based anodes for solid-state lithium-ion batteries disclosed herein may have the following 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, atomic and molecular compositions ("disclosed formulas") provided herein are exemplary only. Those skilled in the art will appreciate that variations in the disclosed formulas may provide compromises for the disclosed high energy density lithium metal-based solid-state anodes 111 for solid-state batteries 100 and may be substituted to achieve similar advantages as the high energy density lithium metal-based anodes for solid-state lithium-ion batteries disclosed herein. In addition, it is expected that various considerations may be considered with respect to battery manufacturing due to variations in materials and manufacturing techniques, including but not limited to polymers, alloys, metals, assembly, tabs, welding, atmospheric composition, etc. and combinations thereof. Still, while the inventors have considered various methods of manufacturing and assembling batteries to achieve one or more of the results of greater storage capacity per mass (energy density), providing high operating current, increasing the durability and life of the battery, increasing the range over which the battery can operate reliably, providing safer batteries, and more efficient production methods, the present disclosure is not limited to the specific components, benefits listed and described herein, and / or manufacturing methods listed herein.

[0043] The foregoing description and accompanying drawings include illustrative embodiments. Having thus described exemplary embodiments, it should be noted by those skilled in the art that the disclosure herein is merely exemplary and that various other alternatives, adaptations, and modifications may be made within the scope of the present disclosure. Simply listing or numbering the steps of a method in a certain order does not constitute any limitation on the order of the steps of the method. Having the benefit of the teachings presented in the foregoing description and the associated drawings, many modifications and other embodiments will occur to those skilled in the art to which the present disclosure pertains. Although specific terms may be used herein, they are used in a general and descriptive sense only and not for purposes of limitation. Therefore, the present disclosure is not limited to the specific embodiments shown herein, but is limited only by the appended claims.

Claims

1. A battery, comprising: at least one cathode; at least one anode having a lithiophilic ceramic fiber framework having a plurality of inter-fiber spaces between a plurality of fibers, the at least one anode capable of conducting a plurality of lithium ions along the plurality of fibers and through the plurality of inter-fiber spaces; at least one separator in contact with the at least one cathode and the at least one anode; and a melt-infused conductive lithium foil disposed in the spaces of the interfiber spaces of the lithiophilic ceramic fiber framework; Among them, the lithium-philic ceramic fiber frame, together with the melt-injected conductive lithium foil, forms a current collector within the space between the fibers of the lithium-philic ceramic fiber frame, which can receive additional lithium metal deposits by electrochemical reduction of multiple lithium ions at the interface between the current collector and the lithium-philic ceramic fiber frame, thereby growing the current collector at the interface and within the multiple fiber spaces.

2. The battery according to claim 1, wherein The lithium-philic ceramic fiber framework includes ceramic fiber felt.

3. The battery according to claim 1, wherein The melt-infused conductive lithium foil acts as a current collector within the anode.

4. The battery according to claim 1, wherein The lithiophilic ceramic fibers are coated with metal.

5. The battery according to claim 4, wherein The metal is at least one metal selected from the group consisting of vanadium nitride, lithium-aluminum alloy, gallium, indium, and tin.

6. The battery according to claim 1, wherein The at least one diaphragm is solid.

7. The battery according to claim 1, wherein The lithiophilic ceramic fiber framework further includes a fiber material having a lithiophilic surface coating deposited thereon.

8. The battery according to claim 7, wherein The lithiophilic surface coating is at least one coating from the group of coatings consisting of oxides, nitrides, polymers and ceramics.

9. The battery according to claim 8, wherein The oxide is at least one oxide from the oxide group consisting of niobium oxide, Al2O3+ZnO (AZO), aluminum oxide, indium oxide, zinc oxide, bismuth oxide, magnesium oxide, silicon oxide, gold oxide, iodine oxide and sulfur oxide, and the nitride is at least one nitride from the nitride group consisting of boron nitride and vanadium nitride.

10. The battery according to claim 7, wherein At least 70% of the volume of the lithiophilic ceramic fiber framework comprises open cavities capable of receiving a solid lithium metal deposit of lithium ions.

11. The battery according to claim 1, wherein The lithiophilic ceramic fiber framework is formed from at least one material from the group of materials consisting of ceramic fibers and polymer fibers.

12. The battery according to claim 11, wherein The at least one material includes a group of fibers having a diameter less than 0.5 μm, a length greater than 1 mm, a lithiophilic coating thickness of approximately 10 nm, and arranged to achieve a porosity greater than 70% and a felt thickness of approximately 86 μm.

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

14. The battery according to claim 1, wherein The lithiophilic ceramic fiber framework is solid.

15. A battery comprising: at least one anode according to claim 1; at least one cathode; and A solid separator in contact with the at least one cathode and the at least one anode according to claim 1.

16. The battery according to claim 15, wherein The anode further includes a melt-infused lithium foil disposed in the active material.

17. The battery according to claim 16, wherein The active material is a ceramic fiber framework.

18. The battery according to claim 16, wherein The active material is a polymer fiber framework.

19. The battery according to claim 16, wherein The active material is at least one active material from an active material group consisting of a ceramic fiber framework and a polymer fiber framework, each of the active materials having a lithiophilic coating.

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