Composite solid electrolyte and lithium battery using same

Abstract

The present disclosure relates to a composite solid electrolyte (CSE) for use in various forms of a battery including a self-supporting CSE separator, an electrode-CSE laminate, a current collector-CSE laminate, or a CSE-based mixed ion-electron conductor (MIEC) electrode. The present disclosure also relates to a method of preparing the composite solid electrolyte and a battery using the same. The disclosed CSE has at least one polymer; at least one lithium salt; a solvent plasticizer; at least one inorganic additive particle; a substrate; and one or more liquid or solid additives. The disclosed method of making a CSE provides at least one polymer, at least one lithium salt, a solvent plasticizer, at least one inorganic additive particle, and one or more liquid or solid additives as a liquid slurry, and coats a substrate with the liquid slurry.

Description

[0001] Cross - Reference to Related Applications

[0002] This patent application claims the benefit of priority to U.S. Provisional Patent Application 63 / 380,889, filed on October 25, 2022, and U.S. Patent Application 18 / 492,229, filed on October 23, 2023, the entire contents of which are hereby incorporated by reference.

[0003] Government Support

[0004] According to 35 U.S.C.§202(c)(6), the applicant hereby states that the invention disclosed in this specification was made under U.S. Federal Government support (Department of Defense, Contract No. N6893622C00180), and the U.S. Federal Government has certain rights in this invention. Technical Field

[0005] This disclosure relates to improved battery structures. Specifically, this disclosure relates to lithium rechargeable batteries assembled using a hybrid solid - state electrolyte composed of a combination of one or more polymers, lithium salts, non - lithium salts, solvent plasticizers, active inorganic additives, non - active inorganic additives, and reinforcing phases. The hybrid solid - state electrolyte can be used as a self - supporting separator inside the cell or laminated directly with the battery electrodes. Background Art

[0006] Currently, the state - of - the - art rechargeable Li - ion battery (LIB) cells used in consumer electronics, electric vehicles (EVs), and many other applications consist of three main components: i.) a positive electrode (cathode), which is the original source of lithium and charge within the cell, ii.) a negative electrode (anode), where lithium is temporarily stored when the cell is in a charged state, and iii.) an electrolyte located in the middle of the cell that facilitates the transfer of lithium between the electrodes.

[0007] Since the concept of LIB was born approximately 30 years ago, most of the innovation in LIBs has occurred in the cathode materials of LIBs. Until recently, the LIB cathode has been the main bottleneck regarding the cycle life of the cell (i.e., the number of charge / discharge cycles that the cell can achieve), the charging speed, and the energy density (i.e., the amount of energy stored per unit volume or mass of the cell). However, significant progress in cathode development has helped reverse these trends. Now, most LIBs are composed of high - nickel layered oxide cathodes (such as LiNi 0.8 Mn 0.1 Co 0.1 O2 (NMC811)) or olivine - type electrodes based on LiFePO4 (LFP). The high - nickel layered oxide cathodes achieve excellent charging speeds and energy densities, while the olivine - type electrodes have less - excellent power and energy performance but extremely high stability and cycle life.

[0008] Now, the attention of academic and industrial development has shifted to addressing new roadblocks to LIB performance stemming from the anode and electrolyte. For most of the LIB's history, the LIB has utilized graphite-based anodes. Li + is embedded in the graphite and occupies the free space existing between the layers of the one-dimensional graphene that contains the graphite. For many reasons, graphite anodes have become a technological mainstay, but their main advantage is that Li + can be embedded and de-embedded in the graphite with high efficiency. When paired with a suitable electrolyte, lithium can penetrate in and out of the graphite with little loss. The efficiency of this reversibility of the embedding process is known as the Coulomb efficiency (CE), and is the reason that, under appropriate conditions, prior art LIBs can achieve cycle lives of thousands of charge / discharge cycles with minimal capacity fade.

[0009] However, a new challenge for graphite anodes is their limited specific capacity of ~370 milliampere-hours (mAh) per gram. This is because six carbon atoms within the graphite structure must be allocated to store each Li + ion. If any improvement that contributes to enhancing the total LIB cell energy density is to be observed on the anode side, new materials need to be used. Since embedding is inherently a thermodynamically slow, surface-limited process, embedding also poses an obstacle to increasing the rate at which the LIB can be charged.

[0010] Meanwhile, liquid electrolytes are a source of fire safety risk for current LIBs. LIBs are produced by sandwiching a porous separator between the anode and the cathode. The separator is typically made of a blend of polypropylene (PP) or polyethylene (PE), and its main purpose is to prevent electrode contact. The cathode and anode are also porous, and the pore network of the cathode / separator / anode stack is then infiltrated with a liquid electrolyte. The liquid electrolyte is typically a solution of lithium hexafluorophosphate (LiPF6) or other types of lithium salts in a mixture of carbonate solvents (e.g., ethylene carbonate (EC) and diethyl carbonate (DEC)). The potential safety issues with this system are obvious, as the carbonates are volatile and highly flammable - the liquid electrolyte has a flash point of ~0 °C, above which the vapors of the carbonate form a combustible mixture with air. In a thermal runaway event, heating the LIB cell can trigger a rapid conversion of the electrolyte into gaseous products and the melting of the separator. Eventually, even the cathode and anode become a fuel source, which drives the increasing self-heating of the cell and certain fires and / or explosions.

[0011] LIB manufacturers have made significant progress in mitigating external and internal short circuits through improved quality control and cell design, which reduces the likelihood of thermal runaway being initiated. However, little improvement has been made in mitigating the severity of the fires and heat release of such thermal runaway in the event of its occurrence. Additionally, studies of the electrification of the automotive industry have found that EVs are less likely to catch fire than internal combustion engine (ICE) vehicles, but the consequences of EV fires are significantly more dangerous for their passengers.

[0012] In summary, the sentiment of mass-market consumers demands that EVs be improved in five key criteria all dependent on the battery cells that make up the EV: i.) economy (the battery pack is ~75% of the total cost of an EV), ii.) charging speed, iii.) range per charge (a function of the battery energy density), v.) service life, and v.) safety. Technical requirements have industrially led many to seek to commercialize solid-state batteries (SSBs). SSBs are broadly similar to conventional LIBs but reduce or eliminate the use of liquid electrolytes through replacement with solid-state electrolyte (SSE) materials. The goal behind using SSEs is to reduce the flammability of the materials comprising the cell and enable the use of next-generation anode materials that increase the cell energy density and charging speed.

[0013] SSEs are generally divided into two categories: inorganic SSEs (ceramics) and organic SSEs (polymers). Inorganic SSEs include oxide materials such as lithium lanthanum zirconate (LLZO), and sulfide materials such as argyrodite. In these SSEs, defects in the ceramic lattice facilitate lithium-ion transport, where Li + "jumps" from defect site to defect site in the material. Organic SSEs are synthesized by dissolving a lithium salt in a polymer system such as polyethylene glycol (PEG); ion transport is then mediated by the Arrhenius-dependent motion of polymer segments above the glass transition temperature of the polymer. This segmental chain motion continuously dissociates Li + and binds it to anions to enable its movement in the material.

[0014] Both organic and inorganic SSEs tend to be significantly more electrochemically and thermally stable than liquid electrolytes and can be used to construct cells that remain benign even when short-circuited or subjected to other forms of abuse. Inorganic SSEs tend to provide a broader safety improvement in this regard. Inorganic SSEs also have significantly higher ionic conductivities - typically at least an order of magnitude higher than organic SSEs. Since the anions of the lithium salt migrate concurrently in the polymer, only a fraction of the ion transference in organic SSEs constitutes Li +The fact makes this difference in ion transport performance even more serious; meanwhile, in inorganic SSEs, all ion migrations that occur are Li + . In addition, the combination of relatively high ionic conductivity and Li + migration in inorganic electrolytes promotes high-throughput density, which can pave the way for ultra-fast charging, while organic SSEs lack this ability and will be inferior to the prior art liquid electrolytes.

[0015] However, due to the poor manufacturability of inorganic SSEs, their commercial success to date has been limited. For example, LLZO is produced using ordinary ceramic calcination and sintering processes at high temperatures (>1200 °C). The process is energy-intensive and resource-intensive - additional lithium must be continuously introduced into the LLZO furnace because lithium evaporates at such elevated temperatures.

[0016] LLZO typically must undergo multiple heat treatment / annealing steps to stabilize the crystallinity and grain boundary interfaces of the material and minimize its cracking sensitivity. Even so, LLZO and related inorganic SSE materials have unfavorable mechanical properties, such as limited flexibility and high brittleness. To replace the polyolefin separator in the LIB cell structure, a continuous inorganic SSE phase must be produced and stacked between the anode and the cathode. The cracking tendency of ceramic SSEs means that they must be thicker (50 μm - 70 μm) than conventional separators (8 μm - 25 μm). This harms the energy density and offsets the degree to which the charging rate can be improved because ionic conductivity depends on the material thickness.

[0017] Another major problem plaguing inorganic SSEs is the high resistance at their surfaces. Although ion transport in the bulk of inorganic SSEs may be fast, it is not so at their interfaces. In particular, it is difficult to establish sufficient contact between the SSE separator and the electrodes. In fact, most commercial examples of batteries using inorganic SSEs have employed keeping a liquid electrolyte within the pores of their anodes and cathodes so that it can "lubricate" the interface with the SSE.

[0018] Recently, sulfide SSEs have attracted the attention of academia and industry. Sulfides are mechanically softer and more conformal at the electrode interface than LLZO. However, sulfide SSEs have their own manufacturing and handling challenges. They are unstable in air and are manufactured using toxic hydrogen sulfide gas.

[0019] Another drawback of sulfides is their instability towards lithium metal anodes (LMAs). LMAs are used in lithium metal batteries (LMBs), which have the potential to provide significantly improved energy density performance characteristics compared to prior art LIBs because LMAs have a capacity of over 3000 mAh g -1The theoretical specific capacity. However, due to the high reactivity of metallic lithium, the successful commercial introduction of LMBs has been limited. The liquid electrolyte is rapidly reduced by LMA to form an inactive solid electrolyte interface (SEI) product, resulting in poor cycling ability. Solid-state electrolytes (SSEs) with enhanced electrochemical stability are generally considered an enabling technology for LMBs. However, there are similar interaction problems between sulfide SSEs and LMA as between liquid electrolytes and LMA.

[0020] “Hybrid” or “composite” electrolytes that blend ceramic and polymer SSE phases are considered a way to combine the ion transport properties of the former with the favorable mechanical properties, processability, and electrochemical stability of the latter. Well-described hybrid systems are LLZO in polyethylene oxide (PEO) or LLZO in polyethylene glycol (PEG). In such systems, LLZO particles are dispersed in a continuous PEO / PEG matrix containing a lithium salt. Ion transport occurs in both phases, despite a synergistic effect. For example, the presence of LLZO reduces the glass transition temperature of the surrounding PEO / PEG matrix and provides mechanical reinforcement. However, the ion transport ability of such systems can generally be described as the volume fraction average of the phases: a larger ratio of polymer to ceramic means more ions moving through the organic phase and a lower total ionic conductivity. Summary of the Invention

[0021] The following is an overview of the present disclosure. This overview does not necessarily identify key elements and does not limit the scope of the present disclosure, but merely serves as an introduction to the following description.

[0022] The present disclosure provides a lithium rechargeable battery integrating a novel composite solid electrolyte (CSE).

[0023] The CSE consists of one or more polymers, a lithium salt, a solvent plasticizer, active (intrinsically Li-ion conductive) inorganic additive particles, inactive (not intrinsically Li-ion conductive) inorganic additive particles, a continuous or discontinuous reinforcing phase, and other liquid or solid additives.

[0024] The addition of the solvent plasticizer allows the CSE to be processed in the form of a liquid slurry. The slurry can be applied as a coating to a substrate by various methods, including but not limited to slot coating, spraying, dip coating, doctor blading, etc.

[0025] The substrate to which the CSE slurry is applied can be a reinforcing phase, such as a porous continuous webbing. Such a porous continuous webbing can be a conventional commercial LIB PE, PP, or PE / PP separator or another suitable continuous webbing. The plasticizer can be completely or partially removed from the slurry to cure the CSE phase on and within the webbing to produce a self-supporting CSE separator. Such a membrane can be densified using methods such as calendering. One composition of the CSE slurry can be used on one side of the webbing, while a different composition of the slurry can be used on the other side of the webbing, where the composition is optimized for the electrode that each side of the separator will face.

[0026] The substrate to which the CSE slurry is applied can be a battery electrode, such as a tape composed of an electrode active material, a binder, and a conductive additive coated on a metal foil. The slurry can flow and infiltrate the pore network of the electrode and / or form a unique coating on top of the electrode. A reinforcing webbing can be added to the unique slurry coating on top of the electrode to support a free-standing CSE separator layer. The plasticizer can be completely or partially removed from the slurry to cure the composite solid electrolyte on and within the electrode and on and within the webbing. The electrode-CSE laminate can be densified using methods such as calendering. The electrode-CSE laminate can also be treated with a vacuum encapsulation bag technique to assist the CSE slurry in thoroughly invading the electrode pore network and in fully removing the plasticizer.

[0027] The substrate to which the CSE slurry is applied can also be a current collector. A reinforcing webbing can be added to support the formation of a unique CSE separator layer. The current collector can be a metal foil, such as copper, aluminum, zinc, tin, nickel, magnesium, etc., or a non-metallic material, such as a carbon textile. The current collector can be lithiophilic or lithiophobic, or can be coated with a lithiophilic material, such as zinc oxide nanoparticles. The current collector can be two-dimensional or have a three-dimensional surface morphology or microstructure. The plasticizer can be completely or partially removed from the slurry to cure it on the current collector. The current collector-CSE laminate can be densified using methods such as calendering.

[0028] The substrate to which the CSE slurry is applied can be a current collector with a metallic lithium coating. The metallic lithium coating can be produced by melt-infusion, vapor deposition, electrodeposition, or other methods. Electrodeposition can be done in situ inside a lithium battery cell. The substrate itself can also be a pure lithium metal foil. A reinforcing webbing can be added to support the formation of a free-standing CSE separator layer. The current collector-CSE laminate can be densified using methods such as calendering.

[0029] Electrode active material particles and a conductive additive (such as amorphous carbon particles) can be added to the CSE slurry to form a mixed ion - electron conductor (MIEC) slurry. The MIEC slurry can be coated onto a current collector material, and the plasticizer can be removed completely or partially to cure the CSE matrix and produce a battery electrode. The CSE matrix serves as a binder for the electrode active material and the conductive additive and as a Li + combination of the conductive phase network. A reinforcing ribbon fabric can be added to support the formation of a freestanding CSE separator layer. The CSE - based MIEC electrode can be densified using methods such as calendering.

[0030] The dense or non - dense freestanding CSE separator, electrode - CSE laminate, current collector - CSE laminate, or CSE - based MIEC electrode can additionally be coated on its surface with a lithiophilic material, such as magnesium nanoparticles or metallic lithium. This can be achieved using chemical vapor deposition, electrodeposition, or other methods. Electrodeposition can be done in situ inside a lithium - ion battery cell.

[0031] A rechargeable lithium - ion battery can be assembled by laminating a freestanding CSE separator between the cathode and the anode. A liquid electrolyte can be added to improve ion transport at the interface between the electrode and the separator, and / or if the electrodes are porous and their pore networks are inaccessible to the separator. Different liquid electrolytes can be used on the cathode side and the anode side. A functional interface stabilizer (FIS) can also be added separately to the surfaces of the cathode and / or the anode.

[0032] A rechargeable lithium - ion battery can also be assembled by using an electrode - CSE laminate, a current collector - CSE laminate, or a CSE - based MIEC electrode instead of the electrode and the electrolyte.

[0033] In one aspect, a CSE is disclosed that has at least one polymer, at least one lithium salt, a solvent plasticizer, at least one inorganic additive particle, a substrate, and one or more liquid or solid additives.

[0034] In another aspect, the substrate is a continuous porous ribbon fabric selected from polyethylene, polypropylene, polyolefin, microporous membrane, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / methacrylate copolymer, woven fabric, glass fiber woven fabric, polyethylene terephthalate fiber woven fabric, cellulose, aramid fiber, other organic or synthetic fibers, or combinations thereof.

[0035] In another aspect, the substrate is a battery electrode, such as a conventional battery electrode, or a strip composed of an electrode active material, a binder, and a conductive additive coated on a metal foil.

[0036] On the other hand, a reinforcing ribbon fabric is provided on the battery electrode to support the independent CSE separator layer.

[0037] On the other hand, the substrate is a current collector having at least one of copper, aluminum, zinc, tin, nickel, magnesium, or carbon fabric.

[0038] On the other hand, the current collector can be lithiophilic or lithiophobic, or coated with at least one lithiophilic material selected from zinc oxide nanoparticles and magnesium nanoparticles of metallic lithium, and wherein the current collector has a two-dimensional or three-dimensional surface morphology or microstructure.

[0039] On the other hand, the current collector is a lithium metal foil or a foil coated with metallic lithium.

[0040] On the other hand, the CSE is configured to prevent short circuits of the battery by functioning as an ion-conductive but electron-insulating barrier between the cathode and the anode of the battery cell.

[0041] On the other hand, the CSE alleviates dendritic growth on the anode of the battery cell and prevents dendrites from short-circuiting the battery cell by maintaining the operational rigidity that dendrites cannot penetrate.

[0042] On the other hand, a method for preparing CSE is disclosed, the method having the steps of: providing at least one polymer, at least one lithium salt, a solvent plasticizer, at least one inorganic additive particle, and one or more liquid or solid additives as a liquid slurry, and coating a substrate with the liquid slurry.

[0043] On the other hand, the coating step is performed using at least one of slot coating, spraying, dip coating, and knife coating.

[0044] On the other hand, the method further includes the step of removing the solvent plasticizer from the liquid slurry to solidify the liquid slurry phase on or within the substrate.

[0045] On the other hand, the method further includes the step of coating the second side of the substrate with a second liquid slurry, the second liquid slurry being the same as or different from the first liquid slurry.

[0046] On the other hand, the slurry can penetrate the pore network of the substrate or form a coating on top of the substrate.

[0047] On the other hand, the substrate is a continuous porous ribbon fabric selected from a polypropylene separator, a polyethylene separator, or a polypropylene / polyethylene separator.

[0048] On the other hand, the substrate is a battery electrode, such as a conventional battery electrode, or a strip composed of an electrode active material, a binder, and a conductive additive coated on a metal foil.

[0049] In another aspect, the method further includes the step of providing a reinforcing ribbon fabric on the battery electrode to support the independent CSE separator layer, and wherein the slurry cures on and within the reinforcing ribbon fabric.

[0050] In another aspect, the method further includes the step of vacuum bagging the electrode and the slurry to facilitate thorough intrusion of the slurry into the pore network of the electrode and removal of the plasticizer.

[0051] In another aspect, the method further includes the step of mixing the slurry with electrode active material particles and a conductive additive (such as amorphous carbon particles) to produce a mixed ion - electron conductor (MIEC) slurry.

[0052] In another aspect, the method further includes the step of calendering or other densification methods.

[0053] In another aspect, the method further includes the steps of melt injection, vapor deposition, and electrodeposition.

[0054] In another aspect, a battery is disclosed, the battery having an anode, a cathode, a separator, a current collector, and a functional interface stabilizer, the functional interface stabilizer having an organic non - aqueous solvent and a lithium salt soluble in the organic non - aqueous solvent.

[0055] In another aspect, the non - aqueous solvent includes 1,2 - dimethoxyethane (DME), 1,1,2,2 - tetrafluoroethyl - 2,2,3,3 - tetrafluoropropyl ether (TTE), dimethyl sulfide (DMS), fluoroethylene carbonate (FEC), vinylene carbonate, dimethyl sulfoxide (DMSO), dimethyl methylphosphonate (DMMPh), trimethyl phosphate (TMP), tris(trimethylsilyl) phosphite (TMSPi), dioxolane (DOL), 1,1 - diethoxyethane (DEE), tetrahydrofuran (THF), triphenyl phosphate (TPhP), tris(2,2,2 - trifluoroethyl) orthoformate (TFEO), vinylene carbonate (VC), triethyl phosphate (TEP), sulfolane (SL), methyl 1,1,2,2 - tetrafluoroethyl ether (TFME), methyl - β - L - fucopyranoside (MFB), 1,2 - (1,1,2,2 - tetrafluoroethoxy)ethane, 1,1,2,2 - tetrafluoroethyl - 1H,1H,5H - octafluoropentyl ether, or acetonitrile.

[0056] In another aspect, the lithium salt is selected from at least one of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluoromethanesulfonyl)imide (LiFSI), lithium fluoride (LiF), lithium nitrate (LiNO3), lithium difluoro(oxalato)borate (LiDFOB), lithium iodide (LiI), lithium difluorophosphate (LiPO2F2), or lithium hexafluorophosphate (LiPF6).

[0057] In another aspect, the separator is selected from a polymer membrane or a multi-layer membrane of polyethylene, polypropylene, polyolefin, microporous membrane, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / methacrylate copolymer, woven fabric, glass fiber woven fabric, polyethylene terephthalate fiber woven fabric, cellulose, aramid fiber, other organic or synthetic fibers, ceramic, composite polymer-ceramic solid electrolyte, or a combination thereof.

[0058] In another aspect, the cathode is selected from lithium-containing spinels such as LiNi 0.5 Mn 1.5 O4 (LNMO), olivines such as lithium iron phosphate (LFP), transition metal oxides in the form of LiMeO x (where Me is one or more metals selected from nickel (Ni), cobalt (Co), manganese (Mn), and aluminum (Al), Li and O represent one or more corresponding lithium atoms and oxygen atoms, and x represents the number of oxygen atoms), or other suitable cathode active materials containing lithium or relying on prelithiation.

[0059] In another aspect, the anode is selected from carbon-based materials (including artificial graphite and natural graphite), silicon-based materials (including pure silicon and silicon oxides), silicon-carbon composites, lithium titanate, lithium vanadate, or other related lithium metal oxide anode materials, lithium metal, and lithium metal alloys.

[0060] In another aspect, the anode, separator, and cathode are each one of an electrode-CSE laminate, a current collector-CSE laminate, or a CSE-based MIEC electrode.

[0061] In another aspect, the separator is a porous polyolefin separator that has been coated and / or impregnated with CSE or consists of a self-supporting CSE membrane.

[0062] In another aspect, the impregnation of CSE into the cathode and / or anode and / or the coating thereon may or may not result in an independent CSE separator phase on the surface of the cathode and / or anode.

[0063] In another aspect, the current collector is coated with or impregnated with CSE.

[0064] In another aspect, the current collector has a lithiophilic coating, including but not limited to metallic lithium.

[0065] In another aspect, the current collector is coated with an MIEC slurry to produce an electrode / CSE mixture, where CSE serves as a binder phase and a Li-ion conducting phase, and optionally also serves as an additional independent CSE separator phase on the surface of the MIEC.

[0066] In one aspect of the present teachings, a CSE is disclosed, the CSE having a continuous polymer matrix, a lithium salt dissolved in the polymer matrix, inactive or active inorganic phase particles dispersed in the polymer matrix, and other inorganic or organic additives added to the matrix which may or may not include a mechanically reinforcing phase additive.

[0067] In another aspect of the present teachings, a rechargeable lithium battery is assembled having a separator formed of a self-supporting film made of a CSE.

[0068] In another aspect of the present teachings, a rechargeable lithium battery is assembled having a conventional porous polyolefin separator that has been coated and / or infused with a CSE to produce a self-supporting solid electrolyte film.

[0069] In another aspect of the present teachings, the CSE facilitates the migration of lithium ions.

[0070] In another aspect of the present teachings, a rechargeable lithium battery is assembled having an anode and / or a cathode, wherein the CSE is coated and / or infused on / in the anode or cathode.

[0071] In another aspect of the present teachings, coating or infusing the CSE into and / or onto the cathode and / or anode may or may not produce an independent CSE separator phase on the surface of the cathode and / or anode.

[0072] In another aspect of the present teachings, a rechargeable lithium battery is assembled having one or more current collectors coated and / or infused with a CSE.

[0073] In another aspect of the present teachings, the current collector has a lithiophilic coating which may or may not be metallic lithium.

[0074] In another aspect of the present teachings, the CSE has a lithiophilic coating which may or may not be metallic lithium.

[0075] In another aspect of the present teachings, the CSE contains electrode active material particles and / or conductive additives to form a MIEC.

[0076] In another aspect of the present teachings, a mixed ionic electronic conductor is coated on the current collector to produce an electrode / CSE mixture, where the CSE serves as a binder phase and a Li-ion conducting phase and may or may not serve an additional role as an independent CSE separator phase on the surface of the MIEC.

[0077] In another aspect of the present teachings, a rechargeable lithium battery cell is assembled having a CSE-based MIEC cathode and / or anode.

[0078] In another aspect of the present teachings, the cathode active material is selected from such as LiNi 0.5 Mn1.5 Lithium-containing spinels of O4 (LNMO), olivines such as lithium iron phosphate (LFP), LiMeO x forms of transition metal oxides (where Me is one or more metals selected from nickel (Ni), cobalt (Co), manganese (Mn), and aluminum (Al), Li and O represent one or more corresponding lithium atoms and oxygen atoms, and x represents the number of oxygen atoms), or other suitable cathode active materials containing lithium or relying on prelithiation.

[0079] In another aspect of the present teachings, the anode active material is selected from carbon-based materials including artificial graphite and natural graphite, silicon-based materials including pure silicon and silicon oxides, silicon-carbon composites, lithium titanate, lithium vanadate, or other related lithium metal oxide anode materials, lithium metal, and lithium metal alloys.

[0080] In another aspect of the present teachings, a rechargeable lithium battery cell, wherein the CSE separator, whether a self-supporting film or laminated to an electrode coated with CSE, a current collector coated with CSE, and / or a layer of a CSE-based MIEC electrode, is configured to prevent battery short circuit by acting as an ion-conducting but electron-insulating barrier between the cathode and anode of the cell.

[0081] In another aspect of the present teachings, a rechargeable lithium battery cell, wherein the CSE separator, whether a self-supporting thin film or laminated to an electrode coated with CSE, a current collector coated with CSE, and / or a layer of a CSE-based MIEC electrode, reduces dendrite growth on the anode of the cell and prevents dendrites from shorting out the cell by maintaining an operational stiffness that is impenetrable to dendrites.

[0082] In another aspect of the present teachings, a liquid functional interface stabilizer (FIS) is provided that forms an interface between the CSE / separator layer and the cathode and / or anode, the liquid wetting agent having at least one organic non-aqueous solvent and at least one lithium salt having a molar concentration of from about 0.1 M to about 8 M.

[0083] In another aspect of the present teachings, the FIS comprises at least one of 1,2-dimethoxyethane (DME), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), dimethyl sulfide (DMS), fluoroethylene carbonate (FEC), vinylene carbonate, dimethyl sulfoxide (DMSO), dimethyl methylphosphonate (DMMPh), trimethyl phosphate (TMP), tris(trimethylsilyl) phosphite (TMSPi), dioxolane (DOL), 1,1-diethoxyethane (DEE), tetrahydrofuran (THF), triphenyl phosphate (TPhP), tris(2,2,2-trifluoroethyl) orthoformate (TFEO), vinylene carbonate (VC), triethyl phosphate (TEP), sulfolane (SL), methyl 1,1,2,2-tetrafluoroethyl ether (TFME), methyl-β-L-fucopyranoside (MFB), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane, 1,1,2,2-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether, or acetonitrile.

[0084] In another aspect of the present teachings, the FIS comprises at least one of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluoromethanesulfonyl)imide (LiFSI), lithium fluoride (LiF), lithium nitrate (LiNO3), lithium difluoro(oxalato)borate (LiDFOB), lithium iodide (LiI), lithium difluorophosphate (LiPO2F2), or lithium hexafluorophosphate (LiPF6).

[0085] In another aspect of the present teachings, the FIS forms a solid electrolyte interface on the anode, and the solid electrolyte interface mechanically adheres to the solid-state electrolyte.

[0086] In another aspect of the present teachings, the FIS forms a cathode electrolyte interface on the cathode, and the cathode electrolyte interface mechanically adheres to the solid-state electrolyte.

[0087] In another aspect of the present teachings, due to the mechanical adhesion to the CSE and the low tendency of interface cracking, the FIS can achieve high coulombic efficiency and charge / discharge cycle stability in a rechargeable battery cell even under low uniaxial stack pressure.

[0088] Other features and aspects of the present teachings will become apparent from the following detailed description in conjunction with the accompanying drawings, which illustrate by way of example the features of embodiments according to the present teachings. This summary is not intended to limit the scope of the present teachings. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] FIG. 1 shows the lithium ion transport mechanism in an existing mixed electrolyte system (e.g., lithium lanthanum zirconate (LLZO) in poly(ethylene oxide) (PEO)). Li +Migration is faster in the inorganic phase particles 1 and slower in the continuous polymeric matrix. The ionic transport performance can be approximated as the volume fractions of the ionic conductivities and the Li + transference numbers of the inorganic phase 11 and the organic phase 12, respectively.

[0090] Figure 2 Shows the lithium ion transport mechanism in a mixed composite solid electrolyte having a polyvinylidene fluoride (PVDF) polymer, a lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, a triethyl phosphate (TEP) plasticizer, and a metakaolin inorganic additive. The inorganic particles 21 are shown within the interaction volume of the inorganic / organic interface 22. The continuous Li + transport is shown along the cooperative particle / polymer interface (interaction volume). Although essentially non-Li + conductive, metakaolin associates with LiTFSI and TEP in the "interaction volume" around each metakaolin particle to form a percolation network through the electrolyte bulk, in which Li + coordinates with the double bond oxygen atoms in TEP and the sulfonyl groups of the LiTFSI anions. The interaction volume can be 27 times larger than the metakaolin particle itself. An additional contribution to the ionic transport performance may come from the Lewis acid strength on the surface of metakaolin, which further dissociates TFSI - and enhances Li + migration, as well as the segmental chain motion of the PVDF polymer, which is enhanced by the x-ray amorphousness of metakaolin.

[0091] Figure 3 Shows a self-supporting CSE membrane using a CSE slurry cast onto a commercial porous PE separator reinforced ribbon fabric. The reinforced ribbon fabric is 8 μm thick, and the slurry coating thickness on either side of the ribbon fabric is about 30 μm. The plasticizer is removed from the slurry by vacuum drying at between 80 °C and 100 °C for 40 minutes. The final self-supporting solid electrolyte membrane is 16 μm thick before densification.

[0092] Figure 4 Shows a method and apparatus for casting a CSE slurry onto a porous PE separator. A roll of separator (upper right) is unwound through a tensiometer and then passed between a pull bar and a doctor blade located on top of a glass plate on the coating bed. The slurry is dispensed in front of the doctor blade, which is pushed forward by the pull bar. By this method, the web is placed onto the slurry coating immediately behind the blade.

[0093] Figure 5 Shows a continuous self-supporting CSE membrane fabricated by dip-coating a CSE slurry onto a commercial porous PE separator reinforced ribbon fabric.

[0094] Figure 6 A method and apparatus for dip coating a PE separator reinforced ribbon fabric are shown. After the separator roll is unwound and wound by a tensioner, it is introduced into a CSE slurry bath under a roller. An excess of slurry is removed using a doctor blade, and then the CSE slurry-wetted separator is wound around an aluminum foil substrate by a take-up roll. If there is no in-line oven, the entire wetted separator roll can be placed in a vacuum oven at 80 °C to 100 °C for 12 hours to remove the plasticizer.

[0095] Figure 7 A graph of the residual mass % versus temperature of a dynamic thermogravimetric analysis (TGA) of a self-supporting CSE separator at a heating rate of 10 °C min -1 from room temperature to 500 °C is shown. The self-supporting CSE separator is prepared by doctor-blading 30 μm of CSE slurry onto an 8 μm PE ribbon fabric and varying the drying time from 0 hours to 12 hours. Different mass ratios of volatile components represent different concentrations of residual plasticizer in the self-supporting membrane. Thus, the amount of plasticizer in the product material can be adjusted. The TGA also shows that the material generally has high thermal stability. At 300 °C, the mass residual percentages of the curves from high to low are 6h, 12h, 3h, 1h, 0h.

[0096] Figure 8 A table describing self-supporting CSE separators using different lithium salts, inorganic additives, reinforced ribbon fabrics, and additional additives is shown. The ionic conductivity is measured by first cutting the self-supporting separator into 19 mm diameter disks. The disks are loaded into a Swagelok cell with stainless steel blocking electrodes. Electrochemical impedance spectroscopy is performed at room temperature, and the ionic resistivity (the reciprocal of the ionic conductivity) is determined using the x-intercept of the linear fit of a Nyquest plot from 100 Hz to 100 kHz.

[0097] Figure 9 A scanning electron micrograph of a PE-based CSE membrane is shown, which shows a CSE coating on the underlying PE separator reinforcement.

[0098] Figure 10 A scanning electron micrograph of a woven glass fiber-based CSE separator is shown, where the presence of the CSE matrix in the glass fibers is visible, and a dense continuous coating of CSE formed on the surface of the glass fiber fabric is also visible.

[0099] Figure 11 The overpotential during the galvanostatic cycling of a symmetric coin cell having the following configuration is shown: metal Li strip | (PE-reinforced CSE separator with DMMPh additive) | metal Li strip (with FIS added at the Li metal / separator interface). At 1 mA cm -2At a current density, 200 galvanostatic cycles were carried out, where the cycle was 2 mAh cm -2 of lithium. After more than 850 hours of cycling, no short circuit or increase in overpotential / polarization was observed.

[0100] Figure 12 Shows the charge (circles) and discharge (squares) specific capacities (based on the cathode active material) of a coin cell with the following construction: 2.0 mAh cm -2 NMC811 cathode | Commercial 8 μm PE separator | Lithium metal strip (with a large amount of FIS added as a liquid electrolyte). The first 5 cycles were carried out with symmetric C / 5 charge / discharge, the 6 - 10th cycles were carried out with symmetric C / 2 charge / discharge, the 11 - 15th cycles were carried out with symmetric 1C charge / discharge, the 16 - 20th cycles were carried out with symmetric 2C charge / discharge, and the 21 - 25th cycles were carried out with symmetric C / 5 charge / discharge (all cycles were from 3V to 4.2V).

[0101] Figure 13 Shows the charge (circles) and discharge (squares) specific capacities (based on the cathode active material) of a coin cell with the following construction: 2.0 mAh cm -2 NMC811 cathode | PE - based self - supporting CSE separator | Lithium metal strip (with FIS added to reduce the separator / Li metal interfacial impedance and provide ion transport in the cathode). The first 5 cycles were carried out with symmetric C / 5 charge / discharge, the 6 - 10th cycles were carried out with symmetric C / 2 charge / discharge, the 11 - 15th cycles were carried out with symmetric 1C charge / discharge, the 16 - 20th cycles were carried out with symmetric 2C charge / discharge, and the 21 - 25th cycles were carried out with symmetric C / 5 charge / discharge (all cycles were from 3V to 4.2V). At all C - rates, the coin cell showed a higher specific capacity than the coin cell fabricated with the prior - art PE separator.

[0102] Figure 14 Shows the charge (circles) and discharge (squares) specific capacities (based on the cathode active material) of an 84 mAh 1 - layer pouch cell with the following construction: 3.5 mAh cm -2 LFP cathode | PE - based self - supporting CSE separator | 4.0 mAh cm -2 Natural graphite anode, which has a commercial liquid electrolyte consisting of 1.2 M LiPF6 and 2 wt% vinylene carbonate in ethylene carbonate / ethyl methyl carbonate at 3:7 (w / w) to provide ionic conductivity in the pore network of the electrodes. The electrode chemistry represents a prior - art LIB cell. The battery was cycled between 2.8V and 3.8V with symmetric C / 2 charge / discharge and an external uniaxial compression of 3.38 atm.

[0103] Figure 15 Shows a scanning electron micrograph of Li deposited on a copper foil collected from a button cell having the following construction: metallic Li strip | copper current collector-CSE laminate. The button cell was assembled in a glove box filled with argon and subjected to a current density of 0.2 mA cm -2 which strips 7 mAh of lithium from the Li metal strip and deposits it on the copper foil laminated to the other side of the PE-reinforced CSE. Dense, SEI-free Li metal morphology is highly desirable and represents the ability of the separator to transport and deposit metallic lithium without being reduced, without producing non-active SEI products, and without depositing porous / lithium dendrites.

[0104] Figure 16 Shows a copper foil disk with distinct Li deposition collected from a metallic Li strip | copper current collector-CSE laminate button cell. This deposition was done on the stack of cell components under zero uniaxial compression in a liquid-free button cell, which indicates, for example, a low interfacial resistivity of the separator compared to prior art solid electrolyte separators.

[0105] Figure 17 Shows an electrode-CSE laminate produced by doctor-blading a CSE slurry onto a cathode strip composed of NMC811 active material, carbon black conductive additive, and PVDF binder. A NMC811 loading of 51 mg cm -2 (>10 mAh cm -2 theoretical areal capacity) produces an as-cast cathode with a thickness >200 μm and a porosity of ∼40%. Sufficient slurry was coated on the surface of the strip, and a PE ribbon fabric reinforcement was added to form a unique separator layer on top of the strip. The electrode-CSE laminate was then dried in a vacuum oven at 80 °C to 100 °C for 12 h and densified by rolling.

[0106] Figure 18 Shows a voltage / specific capacity (based on cathode active material) plot of two C / 10 cycles completed by an 18.26 mAh button cell composed of a 51 mg cm -2 electrode-electrolyte laminate and a Li metal strip anode (with a small volume of liquid electrolyte at the interface between the metallic lithium and the separator layer to reduce impedance). A discharge specific capacity of ∼175 mAh g -1 indicates that 88% of the cathode capacity can be reversibly utilized at a current density of ∼1 mA cm -2 based on the theoretical specific capacity of 200 mAh g -1 of NMC811 at 3 V to 4.2 V).

[0107] Figure 19 Shows a CSE slurry coated onto a 17 mg cm -2(2.0 mAh cm -2 Scanning electron micrograph of a cross-section of an electrode-electrolyte laminate produced by coating a (theoretical areal capacity) LNMO cathode tape and drying at 80 °C for 12 h. Although not densified, a very low porosity is visible due to effective intrusion of the electrolyte into the cathode pore network. Deliberate lamination of the unique PE web-reinforced separator layer is also visible.

[0108] Figure 20 Nyquist plots showing two samples of a silicon electrode-CSE laminate. A 100% silicon active material anode tape ~80 μm thick was doctor-bladed with 1000 μm of CSE slurry. The plasticizer was removed in a vacuum oven at 80 °C for 12 h. The electrode-electrolyte laminate was 126 μm thick before calendaring to 98 μm. The electrode-electrolyte laminate was cut into discs and placed between two stainless steel blocking electrodes inside a coin cell. Electrochemical impedance spectra were measured at room temperature from 0.1 Hz to 1 MHz with a 5 mV amplitude.

[0109] Figure 21 Nyquist plot showing a dry (no liquid present) symmetric coin cell with the following configuration: 1 mAh cm -2 NMC811 cathode tape | PE-reinforced CSE separator | metallic Li tape. The self-supporting separator was laminated with the cathode tape, and the stack was calendared together at 60 °C using a roll press. After assembling the cell with a metallic Li tape (triangle), the charge transfer resistance was immediately high due to lack of uniaxial compression and insulating contaminants on the surface of the Li metal tape. After standing at room temperature for 24 h, the impedance decreased (large circle). After standing at 80 °C for another 48 h (and allowing to cool back to room temperature), the impedance decreased further (small circle). Thus, standing and / or heating helps to overcome the high interfacial resistivity between the self-supporting CSE separator and metallic lithium.

[0110] Figure 22 Shows 1 mAh cm -2 Nyquist plot of a NMC811 cathode tape | PE-reinforced CSE separator | metallic Li tape coin cell after cyclic voltammetry. Five consecutive cyclic voltammetry scans were performed at a scan rate of 20 mV s -1 from the open circuit potential ~3 V to 4.2 V and back to 3 V. The impedance decreased with each cycle, indicating that this technique is also effective in reducing the impedance between metallic lithium and the self-supporting CSE separator.

[0111] Figure 23 Shows 1 mAh cm -2 Nyquist plot of a NMC811 cathode tape | PE-reinforced CSE separator | metallic Li tape coin cell after voltage pulses. Six hundred consecutive 10 mA cm -2Current pulses (both positive and negative polarities) are applied to the cell, where each pulse stops once the cell voltage reaches a cut-off value of 5 V or -5 V. After these pulses, the cell impedance further decreases, indicating that this is also a beneficial strategy for reducing the impedance of the interface between Li metal and the self-supporting CSE separator.

[0112] Figure 24 Schematic illustration of a cell design using a CSE-based MIEC. An MIEC slurry containing cathode active material particles 241 is coated on one side of the self-supporting CSE separator 242. This layer is laminated with an aluminum current collector 240. An MIEC slurry coating containing copper microspheres 243 is applied on the other side of the separator 242. The current collector 244 may or may not be laminated to this layer.

[0113] Figure 25 Graph showing the relationship between the thickness of the Li metal layer (x-axis, in μm) deposited on copper microspheres and the volume of Li metal this would represent (y-axis, in μm 3 )). Depositing 5 μm of Li on copper microspheres of 0.33 mg cm -2 will provide a capacity of 2 mAh cm -2 .

[0114] Figure 26 Graph showing the Coulombic efficiency of a button cell having a metal Li strip|copper current collector - CSE laminate (triangles) configuration and another button cell having a Li strip|CSE-based MIEC containing copper microspheres (circles) configuration. Both button cells also contain FIS. The button cells are subjected to galvanostatic cycling at a current density of 1.0 mAcm -2 for an areal capacity of 2 mAh cm -2 at room temperature. The CSE-based MIEC exhibits consistently high Coulombic efficiency over more than 80 cycles, indicating an improvement in lithium deposition / stripping characteristics and reversibility.

[0115] Figure 27 Scanning electron micrograph showing a CSE-based MIEC containing copper microspheres laminated with a carbon current collector. The carbon is 12 μm thick.

[0116] Figure 28 Graph showing a lithium metal coating established on a carbon fabric current collector having a lithiophilic coating. First, a coating of zinc oxide (ZnO) nanoparticles is formed on the carbon fabric by dipping the carbon fabric into a zinc acetate / methanol solution. Then the methanol is removed in a furnace and the zinc acetate is decomposed into ZnO. The lithium metal is melted in a copper crucible in an argon-filled glove box, and the carbon fabric disk coated with ZnO is dipped into the lithium to produce a melt-injected lithium metal coating. The woven carbon fabric has a three-dimensional surface morphology, which increases the specific surface area and thus reduces the effective current density at the surface.

[0117] Figure 29 Shows a button cell with a 2.0 mAh cm -2 Charge (circles) and discharge (squares) specific capacities (based on cathode active material) plots of a button cell constructed with an NMC811 cathode | PE-based self-supporting CSE separator | lithium metal strip (added with FIS). The cell was symmetrically charged / discharged at a 1C rate from 3V to 4.2V at room temperature.

[0118] Figure 30 Shows a button cell with a 2.0 mAh cm -2 Charge (circles) and discharge (squares) specific capacities (based on cathode active material) plots of a button cell constructed with an NMC811 cathode | PE-based self-supporting CSE separator | carbon fabric coated with ZnO by melt injection of metallic Li (with a small volume of liquid added to reduce the separator / Li metal interface impedance and provide ion transport in the cathode). The cell was symmetrically charged / discharged at a 1C rate from 3V to 4.2V at room temperature. The specific capacity is maintained higher than that achieved with a lithium metal strip, indicating improved polarization and charge / discharge hysteresis through the melt-injected ZnO-coated carbon fabric at high current densities.

[0119] Figure 31 Shows a lithium metal layer formed in-situ on the surface of a PE-based CSE self-supporting separator inside a pouch cell by electrodeposition.

[0120] Figure 32 Schematic showing how a lithium metal layer 335 can be electrodeposited in-situ on the surface of a CSE separator 332 in a cell. Deposition of the layer requires a sacrificial Li anode 331, Li seeds 333, and a tab 334. As Figure 33 shown, the Li metal layer 335 grows on the CSE separator 332.

[0121] Figure 33 Is a schematic cross-section of a button cell. Detailed Description

[0122] The present teachings are described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. The following description is for illustrative purposes only and the present teachings should not be limited to these embodiments.

[0123] In the following description, various aspects of the present disclosure are described. For purposes of explanation, specific configurations and details are set forth in order to provide a thorough understanding of the present disclosure. However, it will be apparent to those skilled in the art that the present disclosure may be practiced without the specific details presented herein. Additionally, well-known features may be omitted or simplified so as not to obscure the present disclosure. Referring specifically to the drawings, it should be emphasized that the details shown are by way of example and for purposes of illustrative discussion of the present disclosure only, and are presented in order to provide what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the present disclosure. In this regard, no attempt is made to show the structural details of the present disclosure in more detail than is necessary for a fundamental understanding of the present disclosure, and the description taken with the drawings makes apparent to those skilled in the art how the several forms of the present invention may be embodied in practice.

[0124] The present disclosure does not limit its application to the details of the construction and arrangement of components set forth in the following description or illustrated in the drawings. The present disclosure is applicable to other disclosures and combinations of the present disclosure that may be practiced or carried out in various ways. The terms and expressions employed herein are for descriptive purposes only and should not be regarded as limiting.

[0125] The present disclosure provides efficient and economical methods and mechanisms for improving the cycle life of lithium-ion batteries and thereby provides an improvement for the technical field or energy storage.

[0126] Figure 33 A schematic diagram of a button cell battery is shown, although the present disclosure is not limited to button cell batteries. The button cell battery 330 has a negative electrode housing 331 and a positive electrode housing 338. A spring 332 is located beside the negative electrode housing 331. A separator 335 is sandwiched between a cathode (negative electrode) 333 and an anode (positive electrode) 337.

[0127] Composite solid electrolytes (CSEs) 335a, 335b may be provided on one or both sides of the separator 335. Alternatively, CSEs 334, 336 may be provided on the cathode 333 or anode 337 respectively, or on their current collectors. The compositions of CSE 335a, CSE 335b, CSE 334, CSE 336 may be the same or different.

[0128] Composite solid electrolytes (CSEs) 335a, 335b can incorporate both polymeric and ceramic materials. The ceramic can be either active or inactive, depending on whether it has intrinsic ion transport properties or enhances the ion transport capabilities of the surrounding continuous polymer matrix. CSEs are dense, with low or no porosity, and may or may not contain a lithium salt or a plasticizer material. One type of CSE is a lithium-ion solid ion complex (LISIC), a polymer-ceramic composite solid electrolyte for use in lithium-ion batteries (LIBs) and lithium metal batteries, the polymer-ceramic composite solid electrolyte comprising a silicoaluminate ceramic, a second component including a polyvinylidene fluoride polymer, and a third component including a lithium salt.

[0129] CSEs 335a, 335b can be processed into a liquid slurry by adding a solvent plasticizer, and the liquid slurry can be applied to the surface of a substrate. These substrates can be rechargeable lithium battery separators or other continuous, porous, and mechanically reinforced webs 335, electrodes 333, 337, current collectors thereon, or other components. The plasticizer can then be removed to create a solid, dense CSE phase on top of and within rechargeable lithium battery materials and components.

[0130] CSEs 335a, 335b, 334, 336 are composed of one or more polymers, lithium salts, solvent plasticizers, active (intrinsically lithium-ion conductive) inorganic additive particles, inactive (not intrinsically lithium-ion conductive) inorganic additive particles, continuous or discontinuous reinforcing phases, and / or other liquid or solid additives.

[0131] The polymer can be polyvinylidene fluoride (PVDF), PVDF-co-hexafluoropropylene (HFP), PVDF grafted with functional groups (such as acrylic acid or other functional groups), or other types of fluorinated or non-fluorinated polymers.

[0132] The lithium salt can include one or a combination of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium acetate (LiC2H3O2), or other suitable lithium salts.

[0133] The solvent plasticizer can include one or a combination of triethyl phosphate (TEP), trimethyl phosphate (TMP), dimethylformamide (DMF), dimethylacetamide (DMAC), n-methyl-2-pyrrolidone (NMP), or other suitable liquid solvent plasticizers.

[0134] The active inorganic additives can include one or a combination of lepidolite, lithium lanthanum zirconate (LLZO), or other suitable intrinsically lithium-conductive inorganic additives. LLZO can be doped with tantalum, niobium, aluminum, or other suitable dopants that enhance ionic conductivity or other properties.

[0135] The inactive inorganic additives can include one or a combination of metakaolin, metahalloysite, alumina, silica, or other suitable inactive inorganic additives. The inorganic additives can be modified to increase their x-ray amorphousness, thereby improving the performance of the CSE. For example, metakaolin can be calcined at an optimized temperature of 400 °C to 1200 °C to minimize its crystallinity. To reduce the particle size and increase its surface activity, urea / aqueous solution can be used to exfoliate metakaolin by first soaking the metakaolin particles in the solution and absorbing urea into their interlayer spaces. Subsequently, calcining the urea-intercalated metakaolin particles exfoliates the aluminol / siloxane layers.

[0136] The continuous or discontinuous reinforcing phase can include one or a combination of a porous polyethylene (PE) LIB separator, a porous polypropylene (PP) separator, a porous cellulose ribbon fabric, woven or chopped glass fibers, woven or chopped aramid fibers, a porous polyester ribbon fabric, or other suitable reinforcing materials. The cellulose can be treated with a complex copper hydroxide solution of sodium hydroxide reacted with copper sulfate or other copper salts to functionalize its surface once the CSE is injected, for coordination of the lithium percolation network.

[0137] Other additives can include one or a combination of non-lithium salts such as zinc bis(trifluoromethanesulfonyl)imide, magnesium bis(trifluoromethanesulfonyl)imide, calcium bis(trifluoromethanesulfonyl)imide, or other suitable salts. Other additives can also include one or a combination of flame-retardant liquid solvents such as tris(2-chloroethyl) phosphate (TCP), dimethyl methylphosphonate (DMMPh), or other suitable flame retardants.

[0138] Other additives can also include (2-chloroethyl)phosphonic acid (ethephon), phenylphosphonic acid (PPA), or other suitable phosphonic acids. Ethephon or PPA can be used in combination with lithium acetate or other suitable lithium salts to graft PVDF with lithium organophosphonate salts. For example, lithium acetate will interact with the acidic groups of PPA to form the dilithium salt of PPA. Grafting this salt to PVDF is useful when using a CSE slurry based on a TEP solvent plasticizer and an LLZO active inorganic additive. TEP will have a strong basic interaction with the surface of LLZO, which can dehydrofluorinate PVDF. Grafting of the lithium phosphonate salt prevents dehydrofluorination of PVDF.

[0139] The addition of a solvent plasticizer allows CSE 335a, 335b to be processed in the form of a liquid slurry. The slurry can be applied as a coating to the substrate 335 by various methods, including but not limited to slot coating, spraying, dip coating, knife coating, etc.

[0140] The substrate to which the CSE slurry is applied can be a reinforcing phase, such as a porous continuous ribbon fabric made of the aforementioned reinforcing phase material. The plasticizer can be completely or partially removed from the slurry to cure the CSE on and within the ribbon fabric to produce a self-supporting solid electrolyte membrane. Such a membrane can be densified using methods such as calendering. A composite solid electrolyte slurry of one composition can be used on one side of the ribbon fabric, while a slurry of a different composition can be used on the other side of the ribbon fabric, where the composition is optimized for the electrode pair that each side of the membrane will face.

[0141] The plasticizer can be removed using heating (drying), vacuum drying, mechanical removal (e.g., roll pressing), or phase inversion. Phase inversion exposes the CSE slurry coating to a liquid in which the CSE slurry coating is insoluble. For example, phase inversion can be achieved by immersing the CSE slurry in deionized water. The water can be a saturated lithium salt solution or an unsaturated lithium salt solution to prevent the removal of lithium from the CSE slurry due to proton exchange. Absolute ethanol or other suitable solvents can also be used to prevent proton exchange.

[0142] The substrate to which the CSE slurry is applied can be the battery electrodes 333, 337, such as a tape composed of an electrode active material, a binder, and a conductive additive coated on a metal foil. The slurry can flow and penetrate into the pore network of the electrode and / or form a unique coating on top of the electrode. A reinforcing ribbon fabric can be added to the unique slurry coating on top of the electrode to support the independent separator layer. The plasticizer can be completely or partially removed from the slurry to cure the CSE phase on and within the electrode and the ribbon fabric. The electrode-CSE laminate can be densified using methods such as calendering. The electrode-CSE laminate can also be treated with a vacuum bag encapsulation technique to help the CSE slurry thoroughly penetrate into the electrode pore network and fully remove the plasticizer.

[0143] The current collector can be a metal foil, such as copper, aluminum, zinc, tin, nickel, magnesium, etc., or a non-metallic material, such as a carbon fabric. The current collector can be lithiophilic or lithiophobic, or can be coated with a lithiophilic material, such as zinc oxide (ZnO) nanoparticles. The current collector can be two-dimensional or have a three-dimensional surface morphology or microstructure. A reinforcing ribbon fabric can be added to support the formation of the unique separator layers 335, 335a, 335b. The plasticizer can be completely or partially removed from the slurry to cure it on the current collector. The current collector-electrolyte laminate can be densified using methods such as calendering.

[0144] By first mixing a saturated solution of zinc acetate (or other suitable zinc salt) in methanol (or other suitable solvent), a lithiophilic ZnO nanoparticle coating can be formed on the surface of the current collector. The current collector can be immersed in the solution before being fired in a furnace to decompose the zinc acetate into ZnO nanoparticles.

[0145] The substrate to which the CSE slurry is applied can include current collectors 335a, 335b, 334, 336 having a metallic lithium coating - constituting a lithium metal anode. The metallic lithium coating can be produced by melt injection, vapor deposition, electrodeposition, or other methods. Electrodeposition can be done in - situ inside a lithium - ion battery cell. The substrate itself can also be a pure lithium metal foil. Reinforcing ribbon fabric can be added to support the formation of the free - standing separator layers 335, 335a, 335b. The current collector - CSE laminate can be densified using methods such as rolling.

[0146] In - situ electrodeposition of the metallic lithium coating can be achieved using a sacrificial metallic lithium anode or lithium inventory from a non - sacrificial working electrode.

[0147] A passivating, protective artificial solid electrolyte interface composed of a lithium - zinc complex can be formed on the surface of the metallic lithium coating. This can be achieved by washing the surface of the metallic lithium with a solution of zinc chloride (ZnCl2), Zn(TFSI)2, zinc fluoride (ZnF2), or other suitable zinc salt in tetrahydrofuran (THF), 1,2 - dimethoxyethane (DME), or other suitable solvent, and then rinsing with pure solvent. Due to the reactivity of the metallic lithium surface, the lithium - zinc complex will form spontaneously from such a treatment.

[0148] Electrode active material particles and conductive additives (such as amorphous carbon particles or carbon nanotubes) can be added to the CSE slurry to form a mixed ion - electron conductor (MIEC) slurry. The MIEC slurry can be coated onto the current collector material, and the plasticizer can be removed completely or partially to cure the CSE matrix and produce battery electrodes 333, 334, 336, 337. The CSE matrix serves as both a binder for the electrode active material in the electrode and a + combination of the Li - conducting phase. Reinforcing ribbon fabric can be added to support the formation of the free - standing separator layers 335, 335a, 335b. The CSE - based MIEC electrodes can be densified using methods such as rolling.

[0149] The active material particles in the CSE - based MIEC can be single - crystal or poly - crystal cathode active material particles, the cathode active material particles including LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi A Mn B CoC O2(0 < A < 1, 0 < B < 1, 0 < C < 1, A + B + C = 1), LiNi A Mn B Co C O2(0 < A < 2, 0 < B < 2, 0 < C < 2, A + B + C = 2), LiNi 1-Y Co Y O2(0 ≤ Y < 1), LiCo 1-Y Mn Y O2(0 ≤ Y < 1), LiNi 1-Y Mn Y O2(0 ≤ Y < 1), LiMn 2-Z Ni Z O4(0 < Z < 2), LiMn 2-Z Co Z One or a combination of O4(0 < Z < 2), LiCoPO4, LiFePO4. The cathode active material may include performance-improving dopants such as germanium, titanium, or other dopants.

[0150] The active material particles in the CSE-based MIEC may include one or a combination of graphite anode materials (such as natural graphite, artificial graphite, or other related anode active materials). The active anode material particles may also include one or a combination of silicon anode materials (such as silicon oxides, pure silicon, or other related materials). The CSE-based MIEC may contain a mixture of graphite and silicon-based anode active materials.

[0151] The active material particles in the CSE-based MIEC may include metal microparticles or nanoparticles, including one or a combination of copper, magnesium, zinc, or other suitable metals or metal alloys.

[0152] The active material particles in the CSE-based MIEC, whether cathode active material, anode active material, or metal, may or may not be coated with lithium aluminum titanium phosphate (LATP) or LLZO to improve their stability in the MIEC.

[0153] The dense or non-dense self-supporting CSE separators 335, 335a, 335b, the electrode-CSE laminates 333, 334, 336, 337, the current collector-CSE laminates 333, 334, or the CSE-based MIEC electrodes 334, 336, 335a, 335b may additionally have their surfaces composed of a CSE phase coated with a lithiumophilic material (such as magnesium nanoparticles or metallic lithium). This can be achieved using vapor deposition, electrodeposition, or other methods. Electrodeposition can be performed in situ inside the lithium battery cell using a sacrificial lithium metal electrode or the lithium inventory of a non-sacrificial cathode.

[0154] A rechargeable lithium battery can be assembled by laminating a self-supporting composite solid electrolyte separator between a cathode 333 and an anode 337. A liquid electrolyte or FIS (schematically shown as options 334, 336) can be added to improve ion transport at the interface between the electrodes 333, 337 and the separator 335, and / or if the electrodes are porous and their pore networks are inaccessible to the separator, a liquid electrolyte or FIS (schematically shown as options 334, 336) can be added. Different liquid electrolytes can be used on the cathode 343 side and the anode 337 side.

[0155] A rechargeable lithium battery can also be assembled by using an electrode-CSE laminate, a current collector-CSE laminate, or a CSE-based MIEC electrode instead of an electrode and an electrolyte.

[0156] More specifically, the cathode 337 active material can preferably be a lithium-containing transition metal oxide, spinel, olivine, or disordered rock salt, for example, selected from LiCoO2, LiNiO2, LiMnO2, LiMn2O4, LiNi A Mn B Co C O2 (0 < A < 1, 0 < B < 1, 0 < C < 1, A + B + C = 1), LiNi A Mn B Co C O2 (0 < A < 2, 0 < B < 2, 0 < C < 2, A + B + C = 2), LiNi 1-Y Co Y O2 (0 ≤ Y < 1), LiCo 1-Y Mn Y O2 (0 ≤ Y < 1), LiNi 1-Y Mn Y O2 (0 ≤ Y < 1), LiMn 2-Z Ni Z O4 (0 < Z < 2), LiMn 2-Z Co Z O4 (0 < Z < 2), LiCoPO4, LiFePO4, or a mixture of any one or at least two of these materials.

[0157] The anode 333 of the lithium battery can be made of various materials, including carbon-based materials, lithium metal, silicon-based active materials, and lithium metal oxide materials (such as Li4Ti5O 12(LTO)). Carbon is the most commonly used anode material and can be of low crystallinity or high crystallinity. Low-crystallinity carbon includes soft carbon and hard carbon, while high-crystallinity carbon can be natural graphite, Kish graphite, pyrolytic carbon, carbon fiber based on mesophase pitch, mesophase carbon microspheres, mesophase pitch, or high-temperature sintered carbon derived from petroleum or coal tar pitch. The anode can also contain a binder, such as poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-co-HFP), PVDF, polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyacrylic acid (PAA), or carboxymethyl cellulose (CMC) with styrene-butadiene rubber (SBR).

[0158] The separator 335 in a lithium battery can be made of a common porous polymer membrane. These membranes are made of materials such as ethylene homopolymer, propylene homopolymer, polyethylene / butene copolymer, ethylene / hexene copolymer, or ethylene / methacrylate copolymer, as a single layer or a laminated structure. In some cases, the separator can also be a common porous nonwoven fabric made of materials such as glass fiber or polyethylene terephthalate fiber with a high melting point.

[0159] By varying the composition and proportion of the polymer, solvent plasticizer, lithium salt, active inorganic additive, inactive inorganic additive, reinforcing phase, and other additives, the composite solid electrolyte material can be adjusted to obtain optimized performance. The polymer imparts elastic properties that improve the electrolyte's resistance to internal strain cracking inside the battery cell. Other characteristics of the CSE are flexibility and durability. The CSE used in the present disclosure prevents short circuits caused by dendrites and is thermally stable at >250 °C, which is a much safer alternative to carbonate-based LIB liquid electrolytes.

[0160] Functional interface stabilizers (FIS) can also be added to the surfaces of the anode 333 and / or the cathode 337, respectively. The functional interface stabilizer can include Li + source of migration. Any lithium salt material commonly used in the liquid electrolyte of LIB can be used. The lithium salt can typically be any one material or a mixture of at least two materials selected from the following:

[0161] · Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI),

[0162] · Lithium bis(fluoromethanesulfonyl)imide (LiFSI),

[0163] · Lithium fluoride (LiF),

[0164] · Lithium nitrate (LiNO3),

[0165] · Lithium difluoro(oxalato)borate (LiDFOB),

[0166] · Lithium iodide (LiI),

[0167] · Lithium difluorophosphate (LiPO2F2),

[0168] · Lithium hexafluorophosphate (LiPF6).

[0169] The lithium salt is preferably used in a concentration range of 0.1 M to 8.0 M. If the concentration of the lithium salt is less than 0.1 M, the concentration is low, thereby reducing the performance of the FIS. On the other hand, if the concentration of the lithium salt is greater than 8.0 M, the viscosity of the stabilizer increases, thereby reducing the mobility of lithium ions and reducing the performance at low temperatures.

[0170] The functional interface stabilizer may include an organic solvent. Any ether-based and carbonate-based materials commonly used in electrolytes for lithium-ion rechargeable batteries can be used. The organic compound may include any one material selected from the following or a mixture of at least two materials as representative examples:

[0171] · Ethers, including:

[0172] o 1,2-dimethoxyethane (DME), and / or

[0173] o 1,1-diethoxyethane (DEE),

[0174] · Hydrofluoroethers (HFE), including:

[0175] o Methyl 1,1,2,2-tetrafluoroethyl ether (TFME), and / or

[0176] o 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE),

[0177] o 1,2-(1,1,2,2-tetrafluoroethoxy)ethane,

[0178] o 1,1,2,2-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether,

[0179] · Fluorinated carbonates, including fluoroethylene carbonate (FEC),

[0180] · Organic sulfurs, including:

[0181] o Dimethyl sulfide (DMS),

[0182] o Dimethyl sulfoxide (DMSO), and / or

[0183] o Sulfolane (SL),

[0184] · Phosphates, including:

[0185] o Triethyl phosphate (TEP),

[0186] o Trimethyl phosphate (TMP),

[0187] o Dimethyl methylphosphonate (DMMPh), and / or

[0188] o Triphenyl phosphate (TPhP),

[0189] · Phosphites, including tris(trimethylsilyl) phosphite (TMSPi),

[0190] · Cyclic ethers, including tetrahydrofuran (THF),

[0191] · Fluoroformates, including tris(2,2,2-trifluoroethyl) orthoformate (TFEO),

[0192] · Carbonates, including vinylene carbonate (VC),

[0193] · Nitriles, including acetonitrile,

[0194] · Methyl β-L-fucopyranoside (MFB),

[0195] · Other heterocyclic organic solvents, including dioxolane (DOL).

[0196] In carbonate-based organic solvents, cyclic carbonates such as EC and PC can be preferably used because they have high viscosities, which cause them to exhibit high dielectric constants and thus dissociate lithium salts in FIS. Additionally, if linear carbonates with low viscosities and low dielectric constants (such as DMC and EDC) are mixed with cyclic carbonates in suitable proportions, an FIS with high electronic conductivity can be prepared.

[0197] The FIS for LIB or LMB is injected into an electrode structure having an anode 333, a cathode 337, and a dense, active CSE separator 335 disposed between the anode 333 and the cathode 337, thereby fabricating an LIB or LMB cell. The anode 333 and the cathode 337 can be made of any type of material commonly used to manufacture lithium-ion rechargeable batteries, such as those discussed herein.

[0198] The foregoing description is a specific embodiment of the present disclosure. It should be understood that this embodiment is described for illustrative purposes only, and that those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present disclosure. All such modifications and changes are included within the scope of the claimed invention or its equivalents.

[0199] As used herein, the term “about” means a value typically within ±5%, depending on the circumstances (e.g., -5% for the lower limit of a range and +5% for the upper limit of a range).

Claims

1. Composite solid electrolyte (CSE), comprising: at least one polymer; at least one lithium salt; a solvent plasticizer; at least one inorganic additive particle; a substrate; one or more liquid or solid additives.

2. The composite solid electrolyte (CSE) according to claim 1, wherein the substrate is a continuous porous ribbon fabric selected from polyethylene, polypropylene, polyolefin, microporous membrane, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / methacrylate copolymer, woven fabric, glass fiber woven fabric, polyethylene terephthalate fiber woven fabric, cellulose, aramid fiber, other organic or synthetic fibers, or combinations thereof.

3. The composite solid electrolyte (CSE) according to claim 1, wherein the substrate is a battery electrode, such as a conventional battery electrode, or a strip composed of an electrode active material, a binder, and a conductive additive coated on a metal foil.

4. The composite solid electrolyte (CSE) according to claim 3, further comprising a reinforcing ribbon fabric on the battery electrode to support the independent CSE separator layer.

5. The composite solid electrolyte (CSE) according to claim 1, wherein the substrate is a current collector having at least one of copper, aluminum, zinc, tin, nickel, magnesium, or carbon fabric.

6. The composite solid electrolyte (CSE) according to claim 5, wherein the current collector can be lithiophilic or lithiophobic, or coated with at least one lithiophilic material selected from zinc oxide nanoparticles, magnesium nanoparticles, and metallic lithium, and wherein the current collector has a two-dimensional or three-dimensional surface morphology or microstructure.

7. The composite solid electrolyte (CSE) according to claim 5, wherein the current collector is a lithium metal foil or a foil coated with metallic lithium.

8. The composite solid electrolyte (CSE) according to claim 1, wherein the CSE is configured to prevent short-circuiting of the battery by acting as an ionically conductive but electronically insulating barrier between the cathode and anode of the battery cell.

9. The composite solid electrolyte (CSE) according to claim 1, wherein the CSE slows down dendrite growth on the anode of the battery cell and prevents the dendrites from short-circuiting the battery cell by maintaining an operationally rigid non-penetrable state for the dendrites.

10. A method for preparing a composite solid electrolyte (CSE), comprising: Providing at least one polymer, at least one lithium salt, a solvent plasticizer, at least one inorganic additive particle, and one or more liquid or solid additives as a liquid slurry; Coating the substrate with the liquid slurry.

11. The method for preparing the composite solid electrolyte (CSE) according to claim 8, wherein the coating step is performed using at least one of slot coating, spraying, dip coating, and blade coating.

12. The method for preparing the composite solid electrolyte (CSE) according to claim 8, further comprising a step of removing the solvent plasticizer from the liquid slurry to solidify the liquid slurry phase on or within the substrate.

13. The method for preparing the composite solid electrolyte (CSE) according to claim 8 further comprises the step of coating a second side of the substrate with a second liquid slurry, which is the same as or different from the liquid slurry.

14. The method for preparing the composite solid electrolyte (CSE) according to claim 8, wherein the slurry can infiltrate the pore network of the substrate or form a coating on top of the substrate.

15. The method for preparing the composite solid electrolyte (CSE) according to claim 8, wherein the substrate is a continuous porous ribbon fabric selected from a polypropylene separator, a polyethylene separator, or a polypropylene / polyethylene separator.

16. The method for preparing the composite solid electrolyte (CSE) according to claim 8, wherein the substrate is a battery electrode, such as a conventional battery electrode, or a strip composed of an electrode active material, a binder, and a conductive additive coated on a metal foil.

17. The method for preparing the composite solid electrolyte (CSE) according to claim 14 further comprises providing a reinforcing ribbon fabric on the battery electrode to support the independent CSE separator layer, and wherein the slurry cures on and within the reinforcing ribbon fabric.

18. The method for preparing the composite solid electrolyte (CSE) according to claim 14 further comprises the step of vacuum bagging the electrode and the slurry to promote thorough infiltration of the slurry into the pore network of the electrode and removal of the plasticizer.

19. The method for preparing the composite solid electrolyte (CSE) according to claim 8 further comprises the step of mixing the slurry with electrode active material particles and a conductive additive such as amorphous carbon particles to produce a mixed ion-electron conductor (MIEC) slurry.

20. The method for preparing the composite solid electrolyte (CSE) according to claim 8 further comprises a calendering step.

21. The method for preparing the composite solid electrolyte (CSE) according to claim 8 further comprises the steps of melt injection, vapor deposition, and electrodeposition.

22. A battery, comprising: an anode; a cathode; a separator; a current collector; a functional interface stabilizer having an organic non-aqueous solvent and a lithium salt soluble in the organic non-aqueous solvent.

23. The battery according to claim 22, wherein the non-aqueous solvent comprises at least one of 1,2-dimethoxyethane (DME), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), dimethyl sulfide (DMS), fluoroethylene carbonate (FEC), vinylene carbonate, dimethyl sulfoxide (DMSO), dimethyl methylphosphonate (DMMPh), trimethyl phosphate (TMP), tris(trimethylsilyl) phosphite (TMSPi), dioxolane (DOL), 1,1-diethoxyethane (DEE), tetrahydrofuran (THF), triphenyl phosphate (TPhP), tris(2,2,2-trifluoroethyl) orthoformate (TFEO), vinylene carbonate (VC), triethyl phosphate (TEP), sulfolane (SL), methyl 1,1,2,2-tetrafluoroethyl ether (TFME), methyl β-L-fucopyranoside (MFB), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane, 1,1,2,2-tetrafluoroethyl-1H,1H,5H-octafluoropentyl ether, or acetonitrile.

24. The battery according to claim 22, wherein the lithium salt is selected from at least one of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluoromethanesulfonyl)imide (LiFSI), lithium fluoride (LiF), lithium nitrate (LiNO3), lithium difluoro(oxalato)borate (LiDFOB), lithium iodide (LiI), lithium difluorophosphate (LiPO2F2), or lithium hexafluorophosphate (LiPF6).

25. The battery according to claim 22, wherein the separator is selected from polyethylene, polypropylene, polyolefin, microporous membrane, ethylene / butene copolymer, ethylene / hexene copolymer, ethylene / methacrylate copolymer, woven fabric, glass fiber woven fabric, polyethylene terephthalate fiber woven fabric, cellulose, aramid fiber, other organic or synthetic fiber, ceramic, composite polymer-ceramic solid electrolyte, or a polymer membrane or multilayer film of a combination thereof.

26. The battery according to claim 22, wherein the cathode is selected from lithium-containing spinels such as LiNi 0.5 Mn 1.5 O4 (LNMO), olivines such as lithium iron phosphate (LFP), transition metal oxides in the form of LiMeO x or other suitable cathode active materials containing lithium or relying on prelithiation, in LiMeO x , Me is one or more metals selected from nickel (Ni), cobalt (Co), manganese (Mn) and aluminum (Al), Li and O represent one or more corresponding lithium atoms and oxygen atoms, and x represents the number of oxygen atoms.

27. The battery according to claim 22, wherein the anode is selected from carbon-based materials including artificial graphite and natural graphite, silicon-based materials including pure silicon and silicon oxides, silicon-carbon composites, lithium titanate, lithium vanadate, or other related lithium metal oxide anode materials, lithium metal, and lithium metal alloys.

28. The battery according to claim 22, wherein the anode, the separator, and the cathode are each one of an electrode-CSE laminate, a current collector-CSE laminate, or a CSE-based MIEC electrode.

29. The battery according to claim 22, wherein the separator is a porous polyolefin separator that has been coated and / or impregnated with CSE or consists of a self-supporting CSE membrane.

30. The battery according to claim 22, wherein the coating of CSE injected into the cathode and / or anode and / or onto the cathode and / or anode to produce an independent CSE may or may not produce an independent CSE separator phase on the surface of the cathode and / or anode.

31. The battery according to claim 22, wherein the current collector is coated with or infused with CSE.

32. The battery according to claim 22, wherein the current collector has a lithiophilic coating, including but not limited to metallic lithium.

33. The battery according to claim 22, wherein the current collector is coated with MIEC slurry to produce an electrode / CSE hybrid, wherein the CSE serves as a binder phase and a Li-ion conducting phase, and optionally also serves as an additional independent CSE separator phase on the surface of the MIEC.

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