Electrolyte-derived membranes for electrochemical stabilization of electrodes containing fibrillated polymers

Abstract

The present invention relates to an electrode having a stable film formed from a polymer, a method for providing a stable film, and an electrolyte composition capable of forming a stable film.

Description

Cross Reference to Related Applications

[0001] This application claims the benefit of priority of U.S. Provisional Application No. 63 / 535,005, filed August 28, 2023, the disclosure of which is incorporated by reference herein in its entirety. TECHNICAL FIELD

[0002] The present invention relates to electrodes formed from TFE-containing polymers having a membrane layer derived from an electrolyte, an electrolyte additive, and a polymer component, and polymer components thereof, methods of making and using the same. BACKGROUND

[0003] Polymers containing PTFE are used as binders for solvent-free electrode casting, which is less expensive and, in some cases, more environmentally friendly than conventional solvent-based electrode casting techniques. Polytetrafluoroethylene (PTFE) has a remarkable ability to fibrillate when shear stress is applied to the polymer. This allows the polymer to be used as a binder in a dry, solvent-free process to form electrodes containing electroactive components and, in some cases, carbon black with the fibrillated polymer. The dry process also allows for the manufacture of higher capacity and thicker electrodes compared to slurry-processed electrodes. These higher capacity electrodes can enable higher energy density lithium ion batteries.

[0004] While polymer binders, including PTFE binders, are electrochemically stable when used in lithium ion battery cathode electrodes, PTFE homopolymers are susceptible to reduction due to their electronic structure when used in anode electrodes. If a PTFE homopolymer is used as a binder in an anode electrode, the mechanical adhesion of the electrode components to the current collector and the cohesion within the electrode will be compromised due to the degradation of the PTFE, which ultimately leads to electrochemical cycling failure. The electrochemical reduction in PTFE also leads to a loss of battery cell capacity due to the loss of cyclable lithium or reversible lithium, and without wishing to be bound by any theory or explanation, it is believed that the homopolymer will produce LiF as well as reduced or partially or fully defluorinated products.

[0005] Accordingly, there is a need for a method of stabilizing electrodes containing polymer components, such as polymer substrates and binders, to prevent the loss of cyclable lithium and to prevent mechanical failure of the electrode during lithium ion battery cycling. SUMMARY

[0006] The present invention relates to electrodes for lithium ion batteries (LiB) and more particularly to electrodes for use as anodes, the electrodes comprising a polymeric component or material, including but not limited to a polymeric substrate, a polymeric binder, a polymeric base structure, with one or more film layers. The polymeric component is selected from the group consisting of, consisting essentially of, or consisting of a TFE-containing fibrillatable polymer, a TFE-containing copolymer, a TFE-containing coagglomerated polymer, or mixtures thereof, alone or in combination with other polymers or fibrillatable polymers.

[0007] In the electrode embodiments disclosed herein, the one or more layers on the polymeric substrate surface or reduced polymeric substrate surface comprise one or more films that are chemically the same or different, independently, and each layer is independently continuous, discontinuous, fragmented.

[0008] In one embodiment disclosed herein, the polymer of the electrode comprises, consists essentially of, or consists of a TFE-containing polymer, a TFE-containing copolymer, and a TFE-containing coagglomerated polymer, wherein the TFE content ranges from 0.1 wt% to 100 wt%, between 0.1 wt% to 90 wt%, or between 0.1 wt% to 95 wt%, and the TFE-containing polymer, copolymer, or TFE-containing coagglomerated polymer is at least partially fibrillated, contains nodes and fibrils, and optionally contains non-fibrillated components.

[0009] In certain embodiments disclosed herein, the polymer of the electrode or on which a film can be formed or deposited comprises, consists essentially of, or consists of one of the following: (1) a TFE-containing fibrillatable polymer; (2) a TFE-containing fibrillatable copolymer; (3) a TFE-containing fibrillatable coagglomerated polymer; (4) a TFE-containing non-fibrillatable polymer, copolymer, or coagglomerated polymer; or (5) a mixture of (i) one of a TFE-containing fibrillatable polymer, copolymer, and coagglomerated polymer and (ii) a TFE-containing non-fibrillatable polymer, wherein fibrillating can include partial fibrillating.

[0010] In certain embodiments disclosed herein, the polymer of the electrode or on which a film can be formed or deposited is optionally free of polyvinylpyrrolidone (PVP).

[0011] In certain embodiments disclosed herein, the polymer of the electrode or on which a film can be formed or deposited is a binder of the electrode and comprises, consists essentially of, or consists of one of: (1) at least partially fibrillated TFE-containing polymer; (2) at least partially fibrillated TFE-containing copolymer; (4) at least partially fibrillated TFE-containing co-condensed polymer, wherein the degree of fibrillation is at least 50%, 60%, 70%, 80%, 90%, 95%, or 100%, and the fibrillated component comprises at least one of nodes and fibrils.

[0012] The one or more film layers associated with the polymer component or material of the electrode are derived from at least one of: decomposition, absorption, assimilation, impregnation, incorporation, polymerization, copolymerization with other electrolyte additives [electrolyte solvents and co-solvents] and polymer electrode components, copolymerization with partially reduced polymers of the polymer component of the electrode, or a combination of one of the polymer component or material of the electrode and an electrolyte composition that includes a mixture of additives in addition to the electrolyte.

[0013] Certain embodiments disclosed herein relate to additives and additive mixtures that are soluble in electrolyte solvents at suitable levels and comprise, consist essentially of, or consist of:

[0014] (a) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with C 1- C4 alkyl groups, and one of:

[0015] (1) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups, or phosphate groups, and optionally fluorine, and

[0016] (2) at least one additive containing at least one unsaturated C=C bond, excluding vinyl carbonate.

[0017] More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises C2 or C3 fluoroolefine carbonate that is unsubstituted or substituted with C 1- C4 alkyl groups, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0018] Certain embodiments disclosed herein relate to an effective amount of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with C 1- C4 alkyl groups, preferably the at least one cyclic additive comprises C2 or C3 fluoroolefine carbonate that is unsubstituted or substituted with C 1-C2 or C3 fluoroolefin carbonate substituted with a C4 alkyl group.

[0019] Certain preferred embodiments disclosed herein are additive mixtures comprising, consisting essentially of, or consisting of (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C 1- C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphonate groups and optional fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or substituted with a C 1- C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphonate groups and optional fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or substituted with a C

[0020] Certain embodiments disclosed herein relate to an additive or additive mixture that is soluble in electrolyte solvents at suitable levels and comprises, consists essentially of, or consists of at least one of (i) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphonate groups and optional fluorine, (ii) at least one additive containing at least one unsaturated C=C bond, or (iii) at least one cyclic additive containing fluorine and carbonyl groups, the additive or additive mixture being selected from one of (i), (i) and (ii), (ii) and (iii), (i) and (iii), or (i), (ii) and (iii), provided that the at least one unsaturated C=C bond optionally excludes ethylene carbonate ethylene (VEC), vinylene carbonate (VC).

[0021]

[0022] Certain embodiments disclosed herein relate to an additive or additive mixture that is soluble in electrolyte solvents at suitable levels and comprises, consists essentially of, or consists of:

[0023] (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphonate groups and optional fluorine, or

[0024] (b) an additive mixture comprising, consisting essentially of, or consisting of (a) and an additional additive selected from one of (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with C 1- C4alkyl groups, and (ii) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate.

[0025] More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2or C3fluoroolefine carbonate that is unsubstituted or substituted with C 1- C4alkyl groups, and (ii) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate.

[0026] Certain embodiments disclosed herein relate to additives and additive mixtures that are soluble in electrolyte solvents at suitable levels, where each additive is independently present in an amount of > 0.05 wt% to the solubility limit of the additive in the electrolyte, including but not limited to 10 wt%, 20 wt%, or 30 wt% of the entire electrolyte composition.

[0027] In one embodiment of the application disclosed herein, the polymeric component constitutes a substrate that can be or can contain a polymeric binder. Electrodes comprising a substrate can be formed by a wet or dry process, i.e., a dry process is carried out without solvents. The polymer of the substrate includes, but is not limited to, a fibrillated polymer, a fluoropolymer, a fibrillated fluoropolymer, a polymer of PTFE and a copolymer of TFE and at least partially fibrillated co-coagulated polymer (a homopolymer of PTFE or a copolymer of TFE co-coagulated with another polymer). Preferably, the polymer includes a fibrillated PTFE homopolymer or a fibrillated polymer containing TFE, a copolymer containing TFE or a homopolymer of PTFE or a copolymer of TFE co-coagulated with another polymer as described herein (a fluoropolymer having a melt creep viscosity different from that of the second polymer). Most preferably, the polymer includes a fibrillated polymer, including but not limited to a homopolymer of PTFE or a copolymer containing TFE or a co-coagulated polymer containing TFE.

[0028] In certain embodiments disclosed herein, the voltage range for forming one or more film layers is 2 V Li / Li + to no more than the decomposition voltage of the polymer; for a PTFE homopolymer, this is approximately 0.6-0.9 V vs. Li / Li +

[0029] ​In certain embodiments disclosed herein, the polymer of the substrate or component of the electrode includes, but is not limited to, TFE-containing polymers and TFE-containing copolymers, each of which is preferably at least partially fibrillated.

[0030] In certain embodiments disclosed herein, the polymer of the substrate or component of the electrode comprises, consists essentially of, or consists of one of the following:

[0031] (a) polyolefins, polyesters, polyamides, polyimides, polyaramides, polyacrylates, polyurethanes, polyethers, polyol ethers, polyacrylonitriles, polyphosphazenes, polysiloxanes, polysulfides, and poly sulfones,

[0032] (b) TFE-containing fibrillated polymers, TFE-containing fibrillated copolymers, non-fibrillated TFE-containing polymers, non-fibrillated TFE-containing copolymers, and mixtures thereof,

[0033] (c) co-condensed fluoropolymers that are fibrillated and non-fibrillated, and mixtures thereof, or

[0034] (d) combinations of (a) and (b), (a) and (c), (b) and (c), or (a), (b), and (c), or preferably TFE-containing polymers that are at least partially fibrillated, TFE-containing copolymers that are at least partially fibrillated, co-condensed TFE-containing copolymers that are at least partially fibrillated.

[0035] In embodiments disclosed herein, the degree of stabilization of the polymer component, substrate, or polymer binder (preferably containing fibril structures) in the electrode is monitored by measuring the scan between or across the voltage range in the presence of an electrolyte composition relative to Li / Li + In the region of 0.9 V to 0.3 V, the first reduction peak is monitored, the electrolyte composition comprising a stabilizing additive selected from one of the following:

[0036] (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups, phosphonate groups, and optionally fluorine, and optionally one of the following: (i) at least one additive containing at least one unsaturated C=C bond and / or (ii) at least one fluorine-containing cyclic additive, or

[0037] (b) an additive mixture comprising, consisting essentially of, or consisting of (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with C 1-C4alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding vinyl carbonate.

[0038] More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C 1- C4alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding vinyl carbonate.

[0039] The measurement can be made using constant current method or using cyclic voltammetry. In some cases, the electrolyte co-solvent such as vinyl carbonate can also have a reduction peak in the region of 0.9 V to 0.3 V. Reducing this reduction peak can also stabilize the electrochemical reaction of the electrolyte on the electrode surface.

[0040] In certain embodiments disclosed herein, the electrolyte composition comprises, consists essentially of, or consists of:

[0041] (a) a solvent containing lithium ions,

[0042] (b) at least one lithium salt additive comprising fluorine and one or more of oxalate, borate, sulfonyl or sulfonimide groups, optionally (i) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC, and / or (ii) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C 1- C4alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding vinyl carbonate. 1- C4alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding vinyl carbonate.

[0043] In certain embodiments, the cyclic additive (iii) comprises difluoroethylene carbonate (DFEC), trifluoropropylene carbonate (TFPC), 4-((2,2,3,3-tetrafluoropropoxy)methyl)-1,3-dioxolan-2-one (HFEEC), and 4-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dioxolan-2-one (NFPEC), most preferably FEC, as shown below:

[0044]

[0045] In preferred embodiments disclosed herein, the additive mixture comprises, consists essentially of, or consists of (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with C 1- C4alkyl groups, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphate groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C 1- C4alkyl groups, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphate groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C

[0046] In certain embodiments disclosed herein, the electrolyte composition includes a phosphate additive comprising, consisting essentially of, or consisting of one or more of lithium tris(oxalato)phosphate (LiTOP) and lithium tetrafluoro(oxalato)phosphate (LiTFOP) and lithium bis(oxalato)difluorophosphate (LiBODFP), wherein the phosphate additive can be used alone or in combination with other additives.

[0047] The present application also relates to a method for forming a film layer derived from an electrolyte composition, such as an electrolyte containing additives, or possibly formed by interaction of a polymer component of an electrode with an electrolyte composition containing at least two additives under an applied voltage, without wishing to be bound by any theory or explanation, the interaction involving decomposition, absorption, assimilation, impregnation, incorporation, polymerization, copolymerization with the electrolyte and / or the additives, especially partial reduction of a polymer of the polymer electrode substrate or polymer component of the electrode, or a combination thereof, wherein the additives are selected from one of (i) at least one lithium salt additive comprising fluorine and one or more of oxalate, borate, sulfonyl or sulfonimide groups or phosphate groups, and (ii) at least one additive containing at least one unsaturated C=C bond or (iii) at least one fluorine-containing cyclic additive, preferably an additive mixture comprising, consisting essentially of, or consisting of (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with C 1-C4alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphate groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises an unsubstituted or C 1- C4alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphate groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises an unsubstituted or C

[0048] In certain embodiments, the electrolyte additive can associate (e.g., impregnate, absorb, incorporate, inhale), react, and / or polymerize with other components of the electrolyte to form a film layer on the electrode or its polymeric components. The film layer can be one or more layers, each of which can be continuous, non-continuous, or discontinuous, stabilizing the polymeric substrate or polymeric components of the electrode from reduction or further reduction. In addition, the film layer can inhibit or reduce electrochemical reactions of the electrolyte on the surface of the electrode.

[0049] In one example, wherein the reduced substrate or polymeric component comprises a fibrillated polymer. According to the present invention, electrochemical reduction in the first reduction scan in a secondary lithium-ion battery is reduced by at least 20% relative to an electrode lacking a polymeric layer derived from an additive mixture comprising (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C 1- C4alkyl group, and one of (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphate groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises an unsubstituted or C

[0050] In some embodiments, electrochemical reduction in the first reduction scan in a secondary lithium-ion battery is reduced by at least 30%, 40%, 50%, 60%, or greater value compared to a battery lacking the inventive additive composition disclosed herein.

[0051] In certain embodiments disclosed herein, the lithium salt additive contains one or more atoms selected from C, B, O, N, and S, preferably the lithium salt additive is selected from at least one lithium salt selected from one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphate groups.

[0052] In some embodiments disclosed herein, the lithium salt additive containing one or more of C, B, O, N and S atoms and optionally fluorine atoms is selected from at least one fluorinated lithium salt, including but not limited to lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium tri(oxalate)phosphate (LiTOP) and LiTFOP (lithium tetrafluoro(oxalate)phosphate), and lithium difluorooxalate difluorophosphate (LiBODFP).

[0053] In some embodiments disclosed herein, the cyclic additive contains fluorine and comprises, is substantially composed of, or is composed of one of the following: ethylene difluorocarbonate (DFEC), propylene trifluorocarbonate (TFPC), 4-((2,2,3,3-tetrafluoropropoxy)methyl)-1,3-dioxolane-2-one (HFEEC), and 4-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dioxolane-2-one (NFPEC).

[0054] In some embodiments disclosed herein, the electrolyte includes, but is not limited to, consists of, or is substantially composed of: lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethyl)tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium perchlorate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate.

[0055] In some embodiments disclosed herein, the lithium salt additive containing lithium, optionally fluorine, one or more of C, B, O, Cl, N and S is selected from at least one fluorinated lithium salt selected from lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LITFSI) and paired with fluoroethylene carbonate (FEC).

[0056] One embodiment disclosed herein relates to a method during the first cycle of a cyclic voltammetry process, relative to Li / Li + Methods for reducing the amplitude of the reduction peak at the anode of a lithium-ion battery and / or reducing the amplitude of the reduction peak at the anode of a lithium-ion battery at voltages of 0.9 volts to 0.3 volts.

[0057] Another embodiment disclosed herein relates to a dry-processed electrode comprising a fibrillated binder capable of reducing and / or decreasing the magnitude of reduction and destabilization of the electrode’s polymer, polymer components, polymer substrate, and / or fibrils.

[0058] Another embodiment disclosed herein relates to a wet-processed electrode comprising a fibrillating binder capable of reducing the magnitude and / or decreasing fibrillation and destabilization of the electrode.

[0059] Another embodiment disclosed herein relates to a dry-processed electrode comprising a fibrillated binder having a membrane formed in the presence of electrons and lithium ions from a lithium salt additive containing lithium, fluorine, and one of carbonate, borate, or sulfonyl groups.

[0060] Another implementation involves making the electrode relative to Li / Li + The amplitude of the reduction peak between 0.9 V and 0.3 V is reduced by at least one of 30%, 40%, 50%, or 60%.

[0061] Another embodiment involves reducing the amplitude of the reduction peak of the electrode by at least 40%, 50%, or 60% by forming a film containing, for example, a decomposition / polymerization / reaction product of a cyclic carbonate.

[0062] Another embodiment involves, optionally in the presence of other electrolyte components, forming one or more films in situ by polymerization or with a reduced polymer substrate or by decomposition or incorporation of a lithium salt additive containing one of lithium, fluorine and carbonate, borate or sulfonyl groups, thereby reducing the amplitude of the reduction peak by at least one of 40%, 50% or 60% at a reduction scan of 0.9 V to 0.3 V.

[0063] Another embodiment involves forming an electrode film from an electrolyte solution, such that the electrode is positioned relative to Li / Li + In the case where the amplitude of the reduction peak between 0.9 V and 0.3 V decreases by at least one of 40%, 50%, or 60%, the electrolyte solution comprises, is substantially composed of, or is composed of the following: an electrolyte containing LiPF6, a straight-chain and / or cyclic carbonate, a fluorinated solvent, and at least one fluorinated lithium salt selected from the following: lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and fluoroethylene carbonate (FEC).

[0064] Another embodiment disclosed herein relates to a composition and method for reducing, preventing, or minimizing the amplitude of reduction peaks in a dry-processed electrode formed with a fibrillated binder by providing and / or forming a membrane layer, wherein the electrolyte contains at least one unsaturated C2-C4 carbonate solvent (excluding VC or VEC) and at least one lithium salt additive selected from lithium salt compounds containing one of fluoride and carbonate, borate, or sulfonyl groups, which may be polymerized, copolymerized, or associated with or incorporated into a membrane on an electrode containing a polymer, the polymer-containing electrode optionally comprising a fibrillated base structure or network.

[0065] One embodiment disclosed herein relates to an additive composition comprising at least one lithium salt compound, substantially consisting of at least one lithium salt compound or consisting of at least one lithium salt compound containing one of carbonate, borate, or sulfonyl groups, for use in obtaining a membrane on an electrode preferably containing a fibrillated basic structure, wherein the amount of the additive composition is from 1% to 10% by weight based on the total amount of the electrolyte solution and the additive composition, wherein the electrolyte solution preferably comprises or consists of LiPF6 in a solvent, substantially consisting of or consisting of LiPF6, wherein the solvent or solvent mixture used for the electrolyte composition may comprise, but is not limited to, substantially consisting of or consisting of: linear carbonates, such as diethyl carbonate, methyl ethyl carbonate, or dimethyl carbonate; cyclic carbonates, such as ethylene carbonate; and fluorinated carbonates, esters, or ethers, or combinations thereof, excluding VEC and VC. Additionally, fluorinated solvents and non-fluorinated solvents, such as non-fluorinated ethers, such as cyclic ether tetrahydrofuran, and fluorinated solvents, such as 2,2-difluoroethyl acetate, fluorinated esters, or 2,2-difluoroethyl methyl carbonate, fluorinated carbonates, may be used. In all cases, the electrolyte may contain more than one solvent, and in many cases, may contain two or more solvents. A preferred mixture comprises an EC / DEC mixture or blend, consisting essentially of an EC / DEC mixture or blend, or consisting of an EC / DEC mixture or blend.

[0066] Another embodiment disclosed herein relates to an electrolyte comprising, substantially comprising, or comprising an electrolyte solution of LiPF6, ethylene carbonate (EC), and diethylene carbonate (DEC), and at least one additive selected from one or more of the following: lithium salt fluorinated additives selected from: lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); fluoroethylene carbonate (FEC); maleic anhydride; and 1-propylene 1,3-sulfonolactone.

[0067] Another embodiment disclosed herein relates to an electrolyte comprising, substantially comprising, or comprising an electrolyte solution of LiPF6, EC, and DEC, and at least one of the following: lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and fluoroethylene carbonate (FEC).

[0068] Another embodiment disclosed herein relates to an electrolyte comprising, substantially comprising, or comprising: solvated LiPF6 in an EC / DEC having a v / v ratio of 2-5:5-8, 1:4 to 2:3 by volume, 1:4 to 5:8 by volume, preferably 3:7 by volume; and a fluoroethylene carbonate (FEC) additive paired with at least one of lithium difluorooxalatoborate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) additives, wherein the corresponding amounts of the electrolyte additives are between 0.05 wt%, >0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt% and the solubility limit of the corresponding additive in the electrolyte, which can be greater than 5 wt%, for example 6 wt%, 7 wt%, 8 wt%, or 9 wt%, or up to and including 10 wt%, 20 wt%, or 30 wt%.

[0069] In other embodiments disclosed herein, the total amount or upper limit of additives contained in the electrolyte is limited by the solubility of the additives in the electrolyte.

[0070] Another embodiment disclosed herein relates to an electrolyte comprising, substantially comprising, or comprising an electrolyte solution of LiPF6, EC, DEC, and additives fluoroethylene carbonate (FEC) and lithium borate oxalate.

[0071] Another embodiment disclosed herein relates to an electrolyte comprising, substantially comprising, or consisting of a LiPF6 electrolyte solution and lithium fluorosulfonylimide as an additive.

[0072] Another embodiment disclosed herein relates to an electrolyte solution comprising, substantially comprising, or comprising: a LiPF6 electrolyte solution, a decomposition additive precursor comprising fluoroethylene carbonate (FEC), and lithium fluorosulfonylimide.

[0073] Another embodiment disclosed herein relates to, but is not limited to, relative to Li / Li +A method for reducing the reduction peak of an electrode within a voltage range of 0.9 volts to 0.3 volts, wherein the electrode comprises one or more materials selected from the following, is substantially composed of one or more materials selected from the following, or is composed of one or more materials selected from the following: silicon, SiO x Lithium alloys such as lithium-aluminum alloys, lithium-lead alloys, lithium-silicon alloys, and lithium-tin alloys; carbon materials such as graphite, graphene, carbon nanotubes, mesophase carbon microspheres (MCMB), and conductive carbon; phosphorus-containing materials such as conductive black phosphorus; metal oxides such as SnO2, SnO, and TiO2; and nanocomposites containing antimony or tin, such as nanocomposites containing oxides of antimony, aluminum, titanium, or molybdenum (see Chem. Mater. 21, 3898-3904). (2009, the disclosure of which is incorporated herein by reference in its entirety) and polymers, preferably optionally polymer binders having a fibrillated structure, the method comprising: contacting an electrode formed of the polymer (or binder) with an electrolyte comprising (i) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine or phosphate, alone or paired with (ii) at least one additive containing at least one unsaturated C=C bond, excluding VC and / or VEC, and (iii) at least one fluorinated cyclic carbonyl additive, wherein the additive is selected from (i), (i) and (ii), (i) and (iii), (ii) and (iii) or (i), (ii) and (iii), wherein the electrode is placed together with a counter electrode in a secondary lithium-ion battery, and at least one scan is performed, wherein the anode potential is from relative to Li / Li + The electrochemical reduction potential should vary by at least 2.0V or higher and should be more positive than that of the polymer binder, and for PTFE homopolymers, the electrochemical reduction potential relative to Li / Li + The voltage is 0.5V to 0.07V, or about 0.6V to about 0.9V, wherein the electrochemical reduction of the polymer and electrolyte is reduced by at least 20% relative to the film prepared without the above-mentioned additive mixture.

[0074] Another embodiment disclosed herein relates to a dry electrode comprising, substantially comprising, or comprising one of the following: graphite, graphene, conductive carbon, metal oxide, SiO2. xThe fluoropolymer binder optionally has an exposed fibrillary structure whose surface is covered, for example, completely or partially covered by a decomposition / polymerization / reaction component product, which is formed from an additive mixture of at least one lithium fluoride salt, such as a carbonate, borate or sulfonylimide, preferably lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI) and maleic anhydride in the presence of a 0.8M, 1.0M, 1.2M or 1.4M LiPF6-EC / DEC solution and optionally fluoroethylene carbonate (FEC).

[0075] Another embodiment disclosed herein relates to a dry electrode comprising, substantially comprising, or comprising of: graphite, graphene, conductive carbon, and a fibrillated fluoropolymer binder, wherein the exposed fibrils / nodes / binder / electrode surfaces are covered by a component product comprising at least two of (a) lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), and maleic anhydride, and (b) fluoroethylene carbonate (FEC).

[0076] Another embodiment disclosed herein relates to a dry electrode comprising, substantially comprising, or comprising of: graphite, graphene, conductive carbon, and at least partially fibrillated fluoropolymer binder, wherein the exposed fibrillary / node surfaces are covered by a polymer film of a decomposition / polymerization / reaction component derived from a LiPF6 solution, the component containing at least two of lithium difluorooxalateborate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), LiTFSI, and fluoroethylene carbonate (FEC).

[0077] One embodiment disclosed herein relates to a method for forming an electrode, the method comprising the steps of: contacting the surface of a graphite electrode containing a fibrillated binder with a LiPF6-EC / DEC solution containing at least two of lithium difluorooxalatoborate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI) or LiTSI and fluoroethylene carbonate (FEC); and applying a voltage range selected from or across one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, 2.0V to 0V, or 2.0V to a lower limit potential, the lower limit potential being more positive than the electrochemical reduction potential of the polymer binder, and for PTFE homopolymers, the electrochemical reduction potential relative to Li / Li + The voltage ranges from 0.6V to 0.9V.

[0078] One embodiment disclosed herein relates to a method for forming a layer on an electrode, the method comprising the steps of: contacting the surface of a graphite electrode containing a fibrillated binder with a decomposition / polymerization / reaction component of a lithium fluoride salt and LiPF6-EC / DEC in the presence of a voltage scan selected from 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V, or 2.0V to a lower limit having a potential more positive than the electrochemical reduction potential of the polymer binder, and for PTFE homopolymers, the electrochemical reduction potential relative to Li / Li + The voltage ranges from 0.6V to 0.9V.

[0079] In some embodiments disclosed herein, the fibrillated binder is a fluoropolymer, such as a copolymer containing PTFE and TFE, preferably wherein the binder comprises, is substantially composed of, or is composed of: a copolymer of PTFE or TFE with one of hexafluoropropylene (HFP) and / or perfluoro(alkyl vinyl ether) (PAVE) (wherein the straight-chain or branched alkyl group contains 1 to 5 carbon atoms), FEP (TFE / HFP copolymer and TFE / HFP / PAVE copolymer), PFA (TFE / PAVE copolymer), wherein PAVE is most preferably perfluoro(ethyl vinyl ether) (PEVE) or perfluoro(propyl vinyl ether) (PPVE), or a combination of perfluoro(methyl vinyl ether) (PMVE) and PPVE, i.e., TFE / PMVE / PPVE copolymer (MFA).

[0080] One embodiment disclosed herein relates to an electrode comprising a fibrillated binder, such as a binder comprising fibrillated PTFE or TFE copolymers, a layer formed in the presence of a scan, and at least one lithium fluoride salt additive preferably as defined herein, the scan spanning a voltage selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V, or the scan spanning a lower voltage limit potential to a potential more positive than the electrochemical reduction potential of the polymer binder, the electrochemical reduction potential relative to Li / Li for PTFE homopolymers. + The range is 0.6V-0.9V (or the sweep voltage lower limit potential is greater than the electrochemical reduction potential of the polymer binder, and for PTFE homopolymers, the electrochemical reduction potential relative to Li / Li). + The voltage is 0.5V to 0.7V, preferably about 0.6V to 0.9V, where “about” is defined as ±1%, ±2% or ±3% of 0.6V, 0.7V, 0.8V or 0.9V.

[0081] Another embodiment disclosed herein relates to a method comprising, substantially comprising, or comprising: applying to a dry-processed graphite electrode containing a polymer binder at least a single scan of a voltage selected from 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V (or a scan across a lower voltage limit potential to a potential more positive than the electrochemical reduction potential of the polymer binder, wherein the electrochemical reduction potential relative to Li / Li for PTFE homopolymers) + (0.6V-0.9V), the graphite electrode is in contact with a LiPF6 solution containing at least two lithium fluoride salt additives, the lithium fluoride salt additives being selected from lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI) or LiTFSI and fluoroethylene carbonate (FEC).

[0082] Another embodiment disclosed herein relates to a dry-processed graphite electrode comprising a fibrillated binder having layers, wherein the electrode is placed in a secondary lithium-ion battery and at least one transvoltage scan is performed to generate layers, wherein the anode potential changes from relative to Li / Li + For at least 2.0V or higher relative to Li / Li + For a voltage range of at least 0V change (or a scan across the voltage range from the lower limit potential to a potential more positive than the electrochemical reduction potential of the polymer binder, or across the voltage range from the lower limit potential to a potential more positive than the electrochemical reduction potential of the polymer binder, for PTFE homopolymer, the electrochemical reduction potential relative to Li / Li + The voltage is 0.5V to 0.7V, preferably about 0.6V to 0.9V), and the electrolyte contains at least one fluorinated additive, wherein "about" is defined as one of ±1%, ±2% or ±3% of 0.6V, 0.7V, 0.8V or 0.9V.

[0083] Another embodiment disclosed herein relates to a graphite electrode comprising a binder, wherein the electrode is placed in a secondary lithium-ion battery and at least one transvoltage scan is performed, wherein the anode potential changes from relative to Li / Li + For at least 2.0V or higher relative to Li / Li + For a scan of potentials from at least 0V change (or across the lower voltage limit to a potential more positive than the electrochemical reduction potential of the polymer binder), the electrochemical reduction potential relative to Li / Li for PTFE homopolymers is... +The voltage is 0.5V to 0.7V, preferably about 0.6V to 0.9V), and the electrolyte contains at least one lithium fluoride salt additive, wherein "about" is defined as one of ±1%, ±2% or ±3% of 0.6V, 0.7V, 0.8V or 0.9V.

[0084] Another embodiment disclosed herein relates to a dry-processed graphite electrode comprising a fibrillated binder having an anti-instability layer and at least a fluorinated additive, the anti-instability layer being formed in the presence of a voltage scan across one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V, and the first scan reduction peak of the electrode at 0.9 to 0.3 volts is minimized or reduced by at least 40%, 50%, or 60%.

[0085] Another embodiment relates to a method for forming a film on an anode electrode containing a fibrillated polymer using an electrolyte in a secondary lithium-ion battery, the electrolyte comprising (i) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine, (ii) at least one additional additive (a) containing at least one unsaturated C=C bond excluding VC and VEC, (b) at least one fluorine-containing cyclic additive, or a combination of (i) and (ii), (ii) and (iii), or (i) and (iii), wherein the electrode is placed in the secondary lithium-ion battery and at least one scan is performed, wherein the anode potential is measured from relative to Li / Li + At least 2.0V or higher relative to Li / Li + At least a 0V change (or a scan across the lower voltage limit to a potential higher than the electrochemical reduction potential of the polymer binder, for PTFE homopolymers, the electrochemical reduction potential relative to Li / Li) + (Voltage is 0.6V-0.9V).

[0086] In some embodiments disclosed herein, at reverse cycling voltages of 0.9 V to 0.3 V, the reduction peak of the electrode containing PTFE or TFE copolymer binder in the lithium electrolyte is reduced by 40% to 70%.

[0087] One embodiment of the invention disclosed herein relates to an adhesive comprising a fibrillated polymer containing PTFE.

[0088] In some embodiments disclosed herein, the fluoropolymer binder of the electrode comprises or is composed of fibrillated or fibrillable PTFE, substantially of or consisting of PTFE.

[0089] In some embodiments disclosed herein, the anode comprises, is substantially composed of, or consists of: graphite active anode powder, Super P conductive carbon, a binder containing PTFE or TFE, and a decomposition / polymerization / reaction component product or polymer layer that prevents / reduces binder reduction and prolongs the lifetime of the anode formed by scanning a voltage applied across a LiPF6 solution containing at least two of lithium difluorooxalatoborate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiTFSI) or LiTSI and fluoroethylene carbonate (FEC), preferably a lithium salt or a lithium salt and FEC.

[0090] In some embodiments disclosed herein, the electrode comprises a polymer on which a film or deposit can be formed, the polymer comprising at least a binder for the electrode, and the electrode comprises, substantially comprises, or comprises the following:

[0091] (a) Materials selected from the following: graphite, graphene, mesophase carbon microspheres (MCMB), silicon or SiOx or mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composites, lithium-ionized tin oxide, conductive black phosphorus, SnO2, SnO, antimony-containing nanocomposites, oxides of aluminum, titanium, and molybdenum, and

[0092] (b) A polymer selected from the following: (1) a TFE-containing fibrillated polymer, (2) a TFE-containing fibrillated copolymer, (3) a TFE-containing fibrillated copolymer, (4) a TFE-containing copolymer that is at least partially fibrillated, or (5) a mixture of one of the TFE-containing fibrillated polymers, copolymers and copolymers with a non-fibrillated TFE-containing polymer, a non-fibrillated TFE-containing copolymer and a non-fibrillated TFE copolymer.

[0093] In some embodiments disclosed herein, the electrode comprises a polymer, film, or deposit, the polymer comprising at least a binder for the electrode, and the electrode comprises, substantially comprises, or comprises: (a) a material selected from: graphite, graphene, mesophase carbon microspheres (MCMB), silicon or SiOx or mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composites, lithium-ionized tin oxide, conductive black phosphorus, SnO2, SnO, antimony-containing nanocomposites, aluminum-titanium and molybdenum oxides, and (b) a polymer selected from: fibrillated TFE polymers, TFE-containing fibrillated copolymers, fibrillated TFE co-condensed polymers, non-fibrillated TFE-containing polymers, copolymers, wherein The fibrillation is partial or complete, and (c) an electrochemically derived and / or initiated membrane formed from an electrode polymer, an electrolyte, and the following materials: (A) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine, optionally at least one additive containing at least one unsaturated C=C bond (excluding VC or VEC) and at least one fluorine-containing cyclic additive, or (B), preferably (B) is an additive mixture comprising, substantially consisting of, or consisting of one of the following: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1- C4 alkyl group substitution, and one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide or phosphate groups and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC.

[0094] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In case of any conflict, this specification and its included definitions shall prevail. Although methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting. Attached Figure Description

[0095] Figure 1 The discharge and charge potential curves of graphite half-cell cells with TE-1 as a binder in EC / EMC and EC / DEC+5% FEC electrolytes are shown for the first cycle.

[0096] Figure 2 SEM scans of the new electrode and the recycled electrode were compared.

[0097] Figure 3 The first comparative voltammetric scan is shown.

[0098] Figure 4 The second comparative voltammetric scan is shown.

[0099] Figure 5 The third comparative voltammetric scan is shown.

[0100] Figure 6 The fourth comparative voltammetric scan is shown.

[0101] Figure 7 The fifth comparative voltammetric scan is shown.

[0102] Figure 8 The baseline X-ray diffraction scan of the electrode components is shown.

[0103] Figure 9 Comparative X-ray diffraction scans of electrolyte additives are shown. Detailed Implementation

[0104] The present invention relates to electrodes made with polymer binders, methods for their preparation, and compositions thereof, wherein at least the fibrils of the binder are protected from instability.

[0105] More specifically, the present invention relates to a membrane derived from an electrolyte solution containing a lithium salt additive, the lithium salt additive being fluorinated and containing one or more of C, B, O, N, and S atoms, which can undergo decomposition / polymerization / reaction during cyclic voltammetry and form a membrane by interacting with one or more of the following: for example, decomposition, absorption, assimilation, impregnation, incorporation, polymerization, copolymerization with other electrolyte additives and components, copolymerization with a partially reduced polymer of a polymer substrate or polymer component of an electrode, or a combination thereof, wherein the membrane reduces the amplitude of the reduction peak during cyclic voltammetry to minimize or prevent instability of the electrode and binder, and stabilizes the electrolyte against reduction on the electrode surface.

[0106] In the electrode embodiments disclosed herein, the one or more layers on the surface of the polymer substrate or the reduced surface of the polymer substrate comprise one or more chemically independent identical or different films, and each layer is independently continuous, discontinuous, or fragmented.

[0107] Before addressing the details of the implementation scheme described herein, some terms are defined or clarified as follows.

[0108] As used herein, the term "electrolyte composition" refers to a chemical composition comprising at least a solvent and an electrolyte salt, wherein the composition is suitable as an electrolyte in an electrochemical battery cell. The electrolyte composition may include other components to enhance the battery's performance in terms of safety, reliability, and / or efficiency.

[0109] As used herein, the term "electrolyte salt" refers to an ionic salt that is at least partially soluble in the solvent of an electrolyte composition and at least partially dissociates into ions in the solvent of the electrolyte composition to form an ionicly conductive electrolyte composition.

[0110] As defined herein, an “electrolyte solvent” is a solvent or solvent mixture used in an electrolyte composition and may include, for example, but not limited to, straight-chain carbonates such as diethyl carbonate, ethyl methyl carbonate, or dimethyl carbonate; cyclic carbonates such as ethylene carbonate; and fluorinated carbonates, esters, or ethers, or combinations thereof. Additionally, fluorinated and non-fluorinated solvents may be used, such as non-fluorinated ethers such as cyclic ether tetrahydrofuran, and fluorinated solvents such as 2,2-difluoroethyl acetate, fluorinated esters, or 2,2-difluoroethyl methyl carbonate, fluorinated carbonates. In all cases, the electrolyte may contain more than one solvent, and in many cases, two or more solvents may be contained.

[0111] The term "anode" refers to the electrode of an electrochemical cell. In a secondary (i.e., rechargeable) battery, the anode is the electrode that is oxidized during discharge and reduced during charging.

[0112] The term "cathode" refers to the electrode of an electrochemical cell unit. In a secondary (i.e., rechargeable) battery, the cathode is the electrode that undergoes reduction during discharge and oxidation during charging.

[0113] The term "lithium-ion battery" refers to a rechargeable battery in which lithium ions move from the anode to the cathode during discharge and from the cathode to the anode during charging.

[0114] As used herein, the terms “derived from” and “produced from” are intended to include, but are not intended to be bound by any theory or interpretation, products, films, layers or deposits formed, in particular, by decomposition, absorption, assimilation, impregnation, incorporation, polymerization, reaction, copolymerization with other electrolyte additives and components, copolymerization with a partially reduced polymer of a polymer substrate or polymer component of an electrode, or combinations thereof.

[0115] "Derived" / "generated" products, films, layers, or deposits are one or more continuous or discontinuous films / layers on a polymer / binder, which may differ from another layer on other electrode components. A derived / generated product, film, layer, or deposit may comprise one or more layers or films, each of which is independently continuous or discontinuous. The polymer substrate or polymer component of the electrode optionally includes a structure comprising one of fibrils and nodes.

[0116] As used herein, fluorinated elastomers include, but are not limited to, repeating units derived from two or more types of monomers, and optionally have curing sites that allow crosslinking to form a three-dimensional network. The first monomer type produces linear fluorinated elastomer segments with a tendency to crystallize. A second monomer type with bulky substituents is incorporated into the fluorinated elastomer chain at intervals to disrupt this tendency to crystallize and produce a substantially amorphous elastomer. Monomers useful for linear segments are those without bulky substituents, and include, but are not limited to, vinylidene fluoride (VDF); CH2=CF2:tetrafluoroethylene (TFE), CF2=CF2:trifluorochloroethylene (CTFE), CF2=CFCl; and ethylene (E), CH2=CH2. Monomers having bulky groups that can be used to disrupt crystallinity include hexafluoropropylene (HFP), CF2=CFCF3; 1-hydropentafluoropropylene, CHF=CFCF3; 2-hydropentafluoropropylene, CF2=CHCF3; perfluoro(alkyl vinyl ethers) (e.g., perfluoro(methyl vinyl) ether (PMVE), CF2=CFOCF3); and propylene (P), CH2=CHCH3, as disclosed in the commonly owned U.S. Patent Publication 2011 / 0200826A1, which is incorporated herein by reference in its entirety. See also A. Moore’s general description of fluorinated elastomers in Fluoroelastomers Handbook: The Definitive User's Guide and Databook, William Andrew Publishing, ISBN 0-8155-1517-0 (2006), which is incorporated herein by reference in its entirety.

[0117] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, condition A or B satisfies any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0118] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those described, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements described in that clause; other elements as a whole are not excluded from the claims.

[0119] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel features of the invention protected by the claims, particularly the mode of action of any process in carrying out the invention to achieve the desired result. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0120] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0121] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0122] Wherever a range of values ​​is given herein, that range is intended to include its endpoints, and all integers and fractions within that range, unless otherwise indicated. When a range is defined, it is not intended to limit the disclosed range to the specific value stated. Furthermore, all ranges described herein are intended to include not only the specific range described, but also any combination of values ​​therein, including the stated minimum and maximum values.

[0123] When a quantity, concentration, or other value or parameter is given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually.

[0124] Wherever a range of values ​​is given in this document, the range is intended to include its endpoints and all integers and fractions within that range, unless otherwise indicated.

[0125] As used in this paper, the equilibrium potential between lithium and lithium ions is achieved by contacting a lithium metal reference electrode with a non-aqueous electrolyte containing a lithium salt at a concentration sufficient to produce approximately 1 mol / L of lithium ions, and subjecting it to a sufficiently small current so that the potential of the reference electrode does not deviate from its equilibrium value (Li / Li). + Significantly altered potential in this type of Li / Li + The reference potential is specified here as 0.0V.

[0126] As used herein, “voltage” refers to the voltage difference between the cathode and anode of a full cell. The electrodes of a full cell cannot operate at a potential of 0.0V relative to Li / Li+. In a half-cell, lithium metal is used as the counter electrode, therefore the counter electrode is at 0.0V relative to Li / Li+.

[0127] As used herein, in some embodiments, the term “about” may be quantified to mean ±1%, ±2%, ±3% of a specified value up to and including ±10%, and all integers and fractions therebetween.

[0128] As used herein, the term "cyclic voltammetry" refers to the principle of linear sweep voltammetry across a voltage potential, a technique for measuring currents that typically change linearly with time during a potential scan. In cyclic voltammetry measurements, the scan across the voltage potential is reversed.

[0129] As used herein, the term “reduction cycle” refers to the first linear scan in a cyclic voltammetry measurement from positive to negative potential or a constant current measurement from positive to negative potential in a lithium-ion battery.

[0130] As used herein, the term “peak amplitude” refers to the maximum peak current observed due to, for example, the decomposition of a polymer or, more specifically, its reduction.

[0131] As used in this article, the term “scan” means “two current-voltage curves with hysteresis generated between two values ​​or across a voltage range between two values.”

[0132] As used herein, the term “fibrillation” means that a polymer is able to form nanofibrils (in at least one dimension, i.e., a width of <100 nm) and that the length of these fibrils can vary from submicrometers to several micrometers or tens of micrometers when the polymer / copolymer is subjected to shear forces, for example.

[0133] As used herein, the term "PTFE-based or TFE-containing" binder means a PTFE homopolymer formed by polymerization of tetrafluoroethylene monomers, or a TFE-containing copolymer containing tetrafluoroethylene (TFE) copolymerized with other monomers.

[0134] In some embodiments disclosed herein, the electrolyte salt includes, but is not limited to, lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethyl)tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium perchlorate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate.

[0135] In some embodiments disclosed herein, lithium salt additives include, but are not limited to, phosphorus-containing compounds such as LiTOP (lithium tri(oxalate)phosphate), LiTFOP (lithium tetrafluoro(oxalate)phosphate), and lithium difluorophosphate (LiBODFP).

[0136] In some embodiments disclosed herein, the electrolyte salt that may be present in the electrolyte composition is selected from one of 0.2M to 2.0M, including but not limited to about 0.3M to about 1.7M, about 0.5M to about 1.2M, or about 0.5M to about 1.7M.

[0137] One concept of the present invention is to provide a lithium battery having a graphite-carbon electrode containing a binder containing PTFE or TFE, the binder being resistant to or resisting the instability of the fibrillated binder in order to substantially maintain the integrity of the fibrillated structure, the binder and the electrode.

[0138] In one embodiment, the binder comprises a tetrafluoroethylene homopolymer, which is essentially composed of repeating units generated from tetrafluoroethylene monomers, as disclosed in U.S. Provisional Application No. 63 / 411,777, filed September 30, 2022, and in existing International Application No. WO 2024 / 072861, published April 4, 2024, entitled “DRY FRIABLE FLUOROPOLYMER AGGLOMERATE COMPOSITIONS FOR USE AS BINDERIN LITHIUM-ION SECONDARY BATTERY ELECTRODES,” the disclosure of which is incorporated herein by reference in its entirety.

[0139] In another embodiment, the tetrafluoroethylene polymer is "modified" PTFE, which refers to a copolymer of tetrafluoroethylene in which the concentration of comonomers is so low that the molecular weight of the resulting polymer does not decrease significantly below that of the homopolymer PTFE. The concentration of such comonomers in the modified PTFE is less than 1% by weight, preferably less than 0.5% by weight. Typically, a minimum amount of at least about 0.05% by weight is used to achieve a significant effect. Examples of comonomers in modified PTFE include perfluoroolefins, particularly hexafluoropropylene (HFP) or perfluoro(alkyl vinyl ether) (PAVE) in which the alkyl group contains one to five carbon atoms (of which perfluoro(ethyl vinyl ether) (PEVE) and perfluoro(propyl vinyl ether) (PPVE) are preferred), trifluorochloroethylene (CTFE), perfluorobutylethylene (PFBE) or other similar monomers that introduce relatively stereo-bulky side groups into the PTFE polymer chain, as disclosed in US 63 / 411,777 and WO 2024 / 072861, which are respectively incorporated herein by reference in their entirety.

[0140] Tetrafluoroethylene polymers or copolymers are fibrillable. Fibrillability means that tetrafluoroethylene polymers can form nanofibrils (in at least one dimension, i.e., a width of <100 nm), and the length of these fibrils can vary from submicrometers to several micrometers or tens of micrometers when subjected to shear forces.

[0141] The fluoropolymer composition of the present invention may contain a second polymer different from the first tetrafluoroethylene polymer. This second polymer is an aqueous dispersion capable of forming fine particles of a size substantially similar to the particle size of the aqueous dispersion of the tetrafluoroethylene polymer, or having solubility in the aqueous phase of the aqueous dispersion of the tetrafluoroethylene polymer, and being able to contact the primary tetrafluoroethylene polymer particles during their aggregation and influence their aggregation to form aggregates.

[0142] In one embodiment, the second polymer includes, but is not limited to, the group consisting of: fluoropolymers (excluding the first polymer (tetrafluoroethylene polymer)), polyolefins, polyesters, polyamides, polyimides, aromatic polyamides, polyacrylates, polyurethanes, polyethers, polyol ethers, polyacrylonitrile, polyphosphazene, polysiloxanes, polysulfides, and polysulfones.

[0143] In one embodiment, the second polymer is selected from the group consisting of: (1) a tetrafluoroethylene polymer having a density of about 0.5 × 10⁻⁶. 11 berthed to approximately 6.0 × 10 11The following are polymers with melt creep viscosity in the range of Poisson's and are different from the first polymer: (2) tetrafluoroethylene perfluoro(alkyl vinyl ether) copolymer (PFA); (3) fluorinated ethylene propylene copolymer (FEP); (4) fluorinated elastomer (FKM); (5) ethylene tetrafluoroethylene copolymer (ETFE); (6) polyvinylidene fluoride polymer (PVDF); (7) polychlorotrifluoroethylene polymer (CTFE); and (8) polyvinyl fluoride (PVF) polymer.

[0144] In one embodiment, the second polymer is a tetrafluoroethylene polymer having a density of about 0.5 × 10⁻⁶. 11 berthed to approximately 6.0 × 10 11 The melt creep viscosity is within the range of Poisson's and is a different tetrafluoroethylene polymer from the tetrafluoroethylene polymer of the first polymer that includes a tetrafluoroethylene polymer.

[0145] In one embodiment, the first polymer comprising the tetrafluoroethylene polymer is a tetrafluoroethylene homopolymer composed of repeating units of tetrafluoroethylene monomers having a density of at least about 3.0 × 10⁻⁶. 11 The melt creep viscosity of the second polymer, which includes a tetrafluoroethylene polymer, is a modified PTFE having a comonomer repeating unit concentration of less than 1% by weight and having at least about 0.5 × 10⁻⁶. 11 Poisson's melt creep viscosity.

[0146] In a preferred embodiment, the second polymer is a tetrafluoroethylene perfluoro(alkyl vinyl ether) (PFA) copolymer. PFA is a copolymer of tetrafluoroethylene (TFE) and perfluoro(alkyl vinyl ether) (PAVE) monomers, wherein the straight-chain or branched perfluoroalkyl groups of the PAVE monomers contain 1 to 5 carbon atoms. Preferred PAVE monomers are those in which the perfluoroalkyl group contains 1, 2, 3, or 4 carbon atoms, respectively referred to as perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), perfluoro(propyl vinyl ether) (PPVE), and perfluoro(butyl vinyl ether) (PBVE). The PFA copolymer can be prepared using several PAVE monomers, such as TFE / perfluoro(methyl vinyl ether) / perfluoro(propyl vinyl ether) copolymers, sometimes referred to in the art as MFA. The PFA may contain about 1% to 15% by weight of PAVE, although when a single PAVE monomer is used to form the PFA, a PAVE content of 2% to 8% by weight, preferably 3% to 5% by weight, is the most common PAVE content, with TFE forming the remainder of the copolymer. In one embodiment, the MFA comprises PMVE, and the composition is about 0.5% to 13% by weight of PMVE and about 0.5% to 3% by weight of PPVE, with the remainder being TFE, reaching a total of 100% by weight. Preferably, the type and amount of PAVE present in the PFA results in a melt temperature greater than about 300°C. The PFA is a fluoroplastic, not a fluoroelastomer. As a fluoroplastic, the PFA is semi-crystalline, i.e., partially crystalline.

[0147] In an alternative embodiment, the second polymer is a perfluorinated ethylene-propylene (FEP) copolymer, specifically a copolymer of tetrafluoroethylene and hexafluoropropylene (HFP). In one embodiment, the HFP content in the FEP is from about 5% to about 17% by weight. In another embodiment, the FEP fluoropolymer comprises a TFE / HFP / PAVE terpolymer, wherein the HFP content is from about 5% to about 17% by weight, and the PAVE content (preferably PEVE) is from about 0.2% to about 4% by weight, with the remainder being TFE, to achieve a total of 100% by weight of fluoropolymer. In one embodiment, to reduce the number of thermally unstable end groups (e.g., carboxylic acid end groups), the FEP fluoropolymer may be subjected to fluorination. This fluorination can be performed by known methods using a variety of compounds that generate fluorine radicals under a variety of conditions known in the art, as discussed earlier herein with respect to PFA.

[0148] In one embodiment, the second polymer is selected from the group consisting of fluorinated elastomers: (1) vinylidene fluoride / hexafluoropropylene copolymer (VDF / HFP); (2) vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer (VDF / HFP / TFE); (3) vinylidene fluoride / perfluoro(methyl vinyl ether) / tetrafluoroethylene copolymer (VDF / PMVE / TFE); (4) tetrafluoroethylene / perfluoro(methyl vinyl ether) copolymer (TFE / PMVE); (5) tetrafluoroethylene / propylene copolymer (TFE / P); and (6) ethylene / tetrafluoroethylene / perfluoro(methyl vinyl ether) copolymer (E / TFE / PMVE).

[0149] In a preferred embodiment, the FKM fluorinated elastomer of the present invention is a copolymer of vinylidene fluoride, more preferably a copolymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene.

[0150] In some embodiments disclosed herein, the materials used for the adhesive include:

[0151] -PFA1: A copolymer of tetrafluoroethylene and perfluoro(propyl vinyl ether) (PPVE), with a PPVE content of 4% by weight, a melt flow rate of 15 g / 10 min, and approximately 200 total carboxylic acid-type unstable end groups per 106 C atoms. Manufactured by Chemours FC LLC.

[0152] -FKM: A copolymer of vinylidene fluoride and hexafluoropropylene (HFP), with an HFP content of 40% by weight and a Mooney viscosity of 114 MU measured at 121°C. Manufactured by Chemours FC LLC.

[0153] -PTFE1: Tetrafluoroethylene homopolymer with a strength of 4.0 × 10⁻⁶ 11 Poisson's melt creep viscosity, manufactured by FC LLC.

[0154] -PTFE3: Modified polymer: Tetrafluoroethylene copolymer containing 0.128% by weight of copolymerized PPVE (perfluoro(propyl vinyl ether)) as a modifier, with a strength of 1.47 × 10⁻⁶. 10 Poisson's melt creep viscosity, manufactured by Chemours FC LLC.

[0155] In some embodiments disclosed herein, the material used for the binder includes the co-bonding compositions described herein and disclosed in Provisional Application 63 / 411,777 (WO 2024 / 072861), including but not limited to the following.

[0156] -PTFE1+10%PFA1: A co-condensed composition containing 95% by weight PTFE1 and 10% by weight PFA1.

[0157] -PTFE2: A modified tetrafluoroethylene polymer containing 0.018 wt% copolyester PFBE (perfluorobutylene) and 0.016 wt% HFP (hexafluoropropylene) modifier, with a strength of 1.5 × 10⁻⁶. 11 The melt creep viscosity of Poisson, manufactured by Chemours FCLLC.

[0158] -PTFE2+5%PFA1: A co-condensed composition containing 95% by weight PTFE2 and 5% by weight PFA1.

[0159] -PTFE2+10%PFA1: A co-condensed composition containing 95% by weight PTFE2 and 5% by weight PFA1.

[0160] -PTFE2+ (polymer of vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene).

[0161] -PTFE3: A modified tetrafluoroethylene polymer containing 0.128% by weight of copoly(PPVE) (perfluoro(propyl vinyl ether)) as a modifier, with a strength of 1.47 × 10⁻⁶. 10 Poisson's melt creep viscosity, manufactured by Chemours FC LLC.

[0162] -PTFE3+5%PFA1: A co-condensed composition containing 95% by weight PTFE3 and 5% by weight PFA1.

[0163] -PTFE3+10%PFA1: A co-condensation composition containing 95% by weight PTFE3 and 10% by weight PFA1.

[0164] -PTFE3+5%FKM: A co-condensed product containing 95% by weight PTFE3 and 5% by weight FKM (a copolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene), or

[0165] -PTFE4: A modified tetrafluoroethylene polymer containing 0.038% by weight of copolymerized PFBE (perfluorobutylethylene) as a modifier, with a composition of 9.16 × 10⁻⁶. 10 Poisson's melt creep viscosity, manufactured by Chemours FC LLC.

[0166] The first electrode embodiment of the present invention disclosed herein comprises, is substantially composed of, or consists of the following:

[0167] A self-supporting / self-standing electrode, comprising, substantially consisting of, or consisting of the following:

[0168] An adhesive having at least partially fibrillated exposed surfaces, the adhesive being selected from at least one of a TFE homopolymer, a TFE copolymer, or a coagulated first TFE-containing copolymer and various second TFE-containing copolymers.

[0169] At least one binder-electrolyte-derived layer on the exposed surface, which reduces the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V when using the electrode in cyclic voltammetry measurements at 25 °C, the electrolyte comprises, is substantially composed of, or is composed of the following:

[0170] (a) Non-aqueous electrolyte solvent,

[0171] (b) a first additive, which comprises, is substantially composed of, or is composed of:

[0172] (1) An effective amount of at least one lithium salt additive, the lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine, and optionally a second additive, or

[0173] (2) An effective amount of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C-substituted. 1- C4 alkyl groups are substituted, and preferably the at least one cyclic additive contains unsubstituted or C4 alkyl groups. 1- The C2 or C3 fluoroolefin carbonate with C4 alkyl group substitution, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC), and at least one third additive.

[0174] The second additive comprises, substantially comprises, or comprises: (a) an effective amount of at least one compound containing an unsaturated C=C bond, the compound comprising 1-propene 1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding VEC and VC; or (b) an effective amount of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C=C bonded. 1- C4 alkyl groups are substituted, and preferably the at least one cyclic additive contains unsubstituted or C4 alkyl groups. 1-C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably the at least one cyclic additive comprising fluoroethylene carbonate (FEC), and the third additive comprising effective amounts of at least one of the following, substantially comprising effective amounts of at least one of the following, or comprising effective amounts of at least one of the following: (a) at least one compound containing an unsaturated C=C bond, the compound comprising 1-propylene 1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding VEC and VC, and (b) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimides and optionally fluorine. The second electrode embodiments disclosed herein according to the invention comprise, substantially comprise, or comprise the following:

[0175] An adhesive having at least partially fibrillated exposed surfaces, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers.

[0176] At least one binder-electrolyte-derived layer on the exposed surface reduces the amplitude of the reduction peak when using electrodes in cyclic voltammetry measurements at 25°C.

[0177] Non-aqueous electrolyte solvents

[0178] An effective amount of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1- C4 alkyl groups are substituted, and preferably the at least one cyclic additive contains unsubstituted or C4 alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably the at least one cyclic additive comprising fluoroethylene carbonate (FEC), and

[0179] The additional components are selected from at least the following: (1) at least one lithium salt additive containing one or more of oxalate, borate or sulfonyl groups or sulfonylimide and optionally fluorine; and (2) at least one additive containing an unsaturated C=C bond, comprising 1-propene 1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate and allyl phenyl carbonate, and free of ethylene carbonate compounds.

[0180] Compared to electrodes lacking the at least one binder-electrolyte-derived layer, the amplitude of the reduction peak of Li / Li+ in cyclic voltammetry measurements was reduced by at least 20% in the range of 0.9 V to 0.3 V.

[0181] The third electrode embodiment of the present invention disclosed herein comprises, is substantially composed of, or consists of the following:

[0182] An adhesive having at least partially fibrillated exposed surfaces, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers.

[0183] At least one binder-electrolyte-derived layer on the exposed surface, which reduces the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V when using an electrode in cyclic voltammetry measurements at 25 °C, the electrolyte comprising:

[0184] A non-aqueous electrolyte solvent, an effective amount of one of LiTFSI, LIDFOB and LiDFOB, and optionally at least one fluorinated cyclic additive, preferably containing a compound of C2 or C3 fluoroolefin carbonate, most preferably fluoroethylene carbonate (FEC).

[0185] Compared to electrodes lacking the at least one binder-electrolyte-derived layer, this electrode exhibits a reduction of at least 40% in the amplitude of the Li / Li+ reduction peak between 0.9 V and 0.3 V in cyclic voltammetry measurements.

[0186] Another electrode embodiment of the present invention disclosed herein comprises, is substantially composed of, or consists of the following:

[0187] An adhesive having at least partially fibrillated exposed surfaces, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers.

[0188] At least one binder-electrolyte-derived layer on the exposed surface, which reduces the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V when using an electrode in cyclic voltammetry measurements at 25 °C, the electrolyte comprising:

[0189] Non-aqueous electrolyte solvents, and

[0190] An effective amount of maleic anhydride, and optionally at least one fluorinated cyclic additive, preferably containing an unsubstituted or substituted C2 or C3 fluoroolefin carbonate compound, most preferably fluoroethylene carbonate (FEC).

[0191] Compared to electrodes lacking the at least one binder-electrolyte-derived layer, the amplitude of the reduction peak of Li / Li+ in cyclic voltammetry measurements was reduced by at least 40% in the range of 0.9 V to 0.3 V.

[0192] In any of the embodiments disclosed herein, the polymeric adhesive comprises one of the following:

[0193] A co-condensation composition containing 95% by weight PTFE1 and 10% by weight PFA1.

[0194] A modified tetrafluoroethylene polymer containing 0.018 wt% copolymer PFBE (perfluorobutylethylene) and 0.016 wt% HFP (hexafluoropropylene) modifier, exhibiting a strength of 1.5 × 10⁻⁶. 11 Poisson's melt creep viscosity

[0195] A co-condensation composition containing 95% by weight PTFE2 and 5% by weight PFA1.

[0196] A co-condensation composition containing 95% by weight PTFE2 and 5% by weight PFA1.

[0197] A co-condensation composition containing >95% by weight of PTFE and up to 5% by weight of FKM.

[0198] The modified tetrafluoroethylene polymer, containing 0.128% by weight of copoly(PPVE) (perfluoro(propyl vinyl ether)) as a modifier, has a strength of 1.47 × 10⁻⁶. 10 Poisson's melt creep viscosity

[0199] A co-condensation composition containing 95% by weight PTFE3 and 5% by weight PFA1.

[0200] A co-condensation composition containing 95% by weight PTFE3 and 10% by weight PFA1.

[0201] A co-condensed product containing 95% by weight PTFE3 and 5% by weight FKM, or

[0202] The modified tetrafluoroethylene polymer, containing 0.038% by weight of copoly(PFBE, perfluorobutylethylene) as a modifier, has a composition of 9.16 × 10⁻⁶. 10 The melt creep viscosity of Poisson, where

[0203] PFA1 is a copolymer of tetrafluoroethylene and perfluoro(propyl vinyl ether) (PPVE), with a PPVE content of 4% by weight, a melt flow rate of 15 g / 10 min, and a per 10 6 The content of approximately 200 unstable end groups of total carboxylic acid types per C atom.

[0204] FKM is a copolymer of vinylidene fluoride, hexafluoropropylene, and tetrafluoroethylene, with an HFP content of 40% by weight and a Mooney viscosity of 114 MU measured at 121°C.

[0205] PTFE1 has a melt creep viscosity of 4.0 × 10⁻⁶. 11 Poiseu's tetrafluoroethylene homopolymer,

[0206] PTFE2 is a modified tetrafluoroethylene polymer containing 0.018% by weight of copolymer PFBE (perfluorobutylene) and 0.016% by weight of HFP (hexafluoropropylene) modifier, and has a strength of 1.5 × 10⁻⁶. 11 Poisson's melt creep viscosity

[0207] PTFE3 is a modified tetrafluoroethylene polymer containing 0.128% by weight of copoly(PPVE) (perfluoro(propyl vinyl ether)) as a modifier, and has a melt creep viscosity of 1.47 × 10⁻⁶. 10 Po, where “about” is defined as including one of ±1%, ±2% or ±3% up to a specified value.

[0208] In other embodiments disclosed herein, the secondary lithium-ion battery, anode, or cathode includes a first electrode, a second electrode, or a third electrode, or one of the other electrodes described above.

[0209] Other embodiments disclosed herein relate to dry electrodes comprising, substantially comprising, or consisting of graphite, graphene, conductive carbon, and fibrillated binders, wherein the exposed fibrils / nodes / binder surfaces are at least partially covered by a polymer formed by the decomposition / polymerization / reaction / electrochemical reduction of components of a composition comprising a lithium electrolyte and an additive mixture, wherein the additive mixture comprises, substantially comprises, or consists of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1- C4 alkyl group substitution; and one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate, wherein (a) is preferably at least one of lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), lithium tri(oxalate) phosphate (LiTOP), lithium tetrafluoro(oxalate) phosphate (LiTFOP), and lithium difluorooxalate difluorophosphate (LiBODFP).

[0210] Another embodiment disclosed herein relates to a dry electrode comprising, substantially comprising, or comprising of: graphite, graphene, conductive carbon, and a fibrillated fluoropolymer binder, wherein the exposed fibrillary surface is covered by a polymer formed by the decomposition / polymerization / reaction of a composition comprising a mixture of components including a lithium electrolyte, at least one unsaturated C2-C4 carbonate solvent, and additives, wherein the additive mixture comprises, substantially comprises, or comprises: at least one cyclic additive component containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1- C4 alkyl group substitution; and the second component: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine, and / or (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate, wherein (a) preferably comprises at least one of lithium difluorooxaloborate (LiDFOB), lithium bis(oxalo)borate (LiBOB) and lithium bis(fluorosulfonyl)imide (LiFSI), and optionally maleic anhydride.

[0211] Another embodiment disclosed herein relates to a dry-processed electrode comprising, substantially comprising, or comprising of graphite, graphene, conductive carbon, and fibrillated fluoropolymer binder, wherein the exposed binder / node / fibril / electrode surface is at least partially covered by a polymer film formed from a LiPF6 solution containing at least two additives selected from lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), or lithium bis(fluorosulfonyl)imide (LiFSI) and fluoroethylene carbonate (FEC), preferably wherein the solution contains an EC / DEC solvent.

[0212] One embodiment disclosed herein relates to a method for forming an electrode, the method comprising the steps of: contacting the surface of a graphite electrode containing a fibrillated binder with a LiPF6 solution containing at least one of lithium difluorooxalatoborate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), and fluoroethylene carbonate (FEC), and applying a scan between or across a voltage range selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V.

[0213] One embodiment disclosed herein relates to a method for forming an anti-destabilization electrode and an electrolyte reduction-stabilized electrode, the method being performed by contacting the surface of a graphite electrode containing a fibrillated binder with a film formed by the interaction of an electrolyte in the presence of a scan within or across a voltage range selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V, or a scan within or across a voltage range from the lower limit potential to a potential more positive than the electrochemical reduction potential of the polymer binder, wherein the electrochemical reduction potential for PTFE homopolymer is relative to Li / Li +The value is 0.6V-0.9V, wherein the fibrillated binder is a fluoropolymer, such as a copolymer containing PTFE and TFE, preferably wherein the binder comprises, is substantially composed of, or is composed of: a copolymer of PTFE or TFE with one of hexafluoropropylene (HFP) and / or perfluoro(alkyl vinyl ether) (PAVE), wherein the straight-chain or branched alkyl group contains 1 to 5 carbon atoms; FEP (TFE / HFP copolymer and TFE / HFP / PAVE copolymer); PFA (TFE / PAVE copolymer), wherein PAVE is most preferably perfluoro(ethyl vinyl ether) (PEVE) or perfluoro(propyl vinyl ether) (PPVE); or a combination of perfluoro(methyl vinyl ether) (PMVE) and PPVE, i.e., TFE / PMVE / PPVE copolymer (MFA).

[0214] Some embodiments disclosed herein relate to a method that includes:

[0215] An electrode is provided comprising, substantially comprising, or comprising: at least partially fibrillated binder having an exposed surface, said binder being selected from at least one of TFE homopolymer, TFE copolymer, or condensed first TFE copolymer and various second TFE copolymers.

[0216] The electrode is brought into contact with an electrolyte, which comprises, substantially consists of, or is composed of the following:

[0217] Non-aqueous electrolyte solvents

[0218] An effective amount of at least one cyclic additive containing fluorine and carbonyl groups, preferably a cyclic fluorocarbon additive, more preferably a C2 or C3 fluoroolefin carbonate, and most preferably a fluoroethylene carbonate (FEC), and

[0219] At least one additional component selected from: at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine; and at least one compound containing an unsaturated C=C bond comprising 1-propene-1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding ethylene carbonate compounds.

[0220] A scan is applied between or across voltage ranges, and a reduction-inhibiting film or deposit is formed on the exposed surface of the electrode.

[0221] The amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V during cyclic voltammetry measurements using electrodes is reduced by at least 20% relative to the film formed in the absence of an effective amount of at least one cyclic fluorocarbonate additive and at least one additional component.

[0222] in:

[0223] Compared to an electrode without the membrane, compared to Li / Li + The amplitude of the reduction peak between 0.9V and 0.3V is reduced by one of 30%, 40%, 50%, 60%, or greater.

[0224] The scan between or across voltage ranges is selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, or 2.0V to 0.6V relative to Li / Li+.

[0225] Some embodiments disclosed herein relate to a method for reducing the electrochemical reduction of an adhesive having at least partially fibrillated exposed surfaces, the adhesive comprising a copolymer containing PTFE or TFE and having a TFE content of at least 90% by weight. The method includes...

[0226] The electrode formed of the polymer is contacted with an electrolyte comprising an effective amount of fluoroethylene carbonate (FEC) and additional components selected from: (1) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine; and (2) at least one compound containing an unsaturated C=C bond comprising 1-propene-1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding ethylene carbonate compounds.

[0227] In (1), the electrode and the counter electrode are placed together in a secondary lithium-ion battery, and at least one scan is performed, wherein when a graphite electrode is used, the anode potential changes from relative to Li / Li + At least 1.0V or higher relative to Li / Li + At least 0.6V or relative to Li / Li + At least a 0.3V change, where the lower limit is relative to Li / Li +(2) The electrochemical reduction of the polymer and electrolyte is reduced by at least 20% relative to the electrode having a membrane produced without the combination of FEC and additional components, or the electrochemical reduction of the electrode and electrolyte in a secondary lithium-ion battery is reduced by 30%, 40%, 50%, 60% or greater.

[0228] In some embodiments disclosed herein, the fluoropolymer binder of the electrode comprises or is composed of fibrillated or fibrillable PTFE, substantially of or consisting of PTFE.

[0229] One embodiment disclosed herein relates to an electrode comprising a fibrillated binder, such as a binder comprising fibrillated PTFE, and a layer formed in the presence of a scan within or across a voltage range selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V, or a scan within or across a voltage range from the lower limit potential of the voltage range to a potential more positive than the electrochemical reduction potential of the polymer binder (for PTFE homopolymers, the electrochemical reduction potential relative to Li / Li) + (0.6V-0.9V) and at least fluorinated additives.

[0230] Another embodiment disclosed herein relates to a method comprising, substantially comprising, or comprising: applying to a dry-processed carbon electrode containing a fibrillated binder at least a single scan within or across a voltage range selected from 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V (or a scan across the voltage range from the lower limit potential to a potential more positive than the electrochemical reduction potential of the polymer binder, for PTFE homopolymers, the electrochemical reduction potential relative to Li / Li + (0.6V-0.9V), the dry-processed carbon electrode is in contact with a LiPF6 solution containing at least two of lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bis(fluorosulfonyl)imide (LiFSI), and fluoroethylene carbonate (FEC).

[0231] Another embodiment disclosed herein relates to a dry-processed carbon electrode comprising a fibrillated binder having an anti-destabilization layer and at least one additive mixture containing a fluorinated additive. This anti-destabilization layer is formed in the presence of a voltage range selected from 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V, or a double scan across such a voltage range, or in the presence of a scan between or across the lower limit of the voltage range potential and a potential more positive than the electrochemical reduction potential of the polymer binder, wherein the electrochemical reduction potential relative to Li / Li for PTFE homopolymers is... + The voltage is 0.6V-0.9V.

[0232] Another embodiment disclosed herein relates to a dry-processed graphite electrode comprising a fibrillated binder with an anti-destabilization layer and an electrolyte reduction-stable electrode. The electrolyte reduction-stable electrode is formed in the presence of a scan within or across a voltage range selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, 2.0V to 0.6V, or 2.0V to 0V, or in the presence of a scan between or across a voltage range lower limit potential to a potential more positive than the electrochemical reduction potential of the polymer binder, wherein the electrochemical reduction potential for PTFE homopolymer is relative to Li / Li + The voltage is 0.6V-0.9V, and at least one lithium fluoride salt additive, such that the amplitude current of the reduction peak is minimized or reduced by at least 40%, 50% or 60% under reverse cycling from 0.2V to 0.9V.

[0233] Other embodiments disclosed herein relate to anodes and batteries, wherein the anode comprises an active material capable of storing and releasing lithium ions. Suitable anode materials include, but are not limited to, lithium titanate, aluminum, platinum, palladium, graphite, graphene, transition metal oxides and lithium-ionized tin oxide carbon materials, such as graphite and mesophase carbon microspheres (MCMB); phosphorus-containing materials, such as conductive black phosphorus; metal oxides, such as SnO2, SnO and TiO2; and antimony or tin-containing nanocomposites, such as nanocomposites containing oxides of antimony, aluminum, titanium or molybdenum, or silicon / carbon / graphite composites and SiOx / carbon / graphite composites.

[0234] In one embodiment disclosed herein, the anode active material comprises graphite, graphene, silicon, or SiO₂. x Or a mixture thereof.

[0235] In some embodiments disclosed herein, an electrolyte containing an anode additive is assembled in a suitable container (not shown) to provide an electrochemical cell unit and a cathode. The casing material is well known in the art and may include, for example, metal and polymer casings. While the shape of the casing is not particularly important, suitable casings can be manufactured in the shape of small or large cylinders, prismatic shells, or pouches. Depending on the type of electrochemical cell unit, the anode and cathode can be made of any suitable conductive material.

[0236] Porous membranes exist and are used to prevent short circuits between the anode and cathode. Porous membranes are typically, but are not limited to, single-layer or multi-layer sheets of microporous polymers, such as polyethylene, polypropylene, polyamide, polyimide, or combinations thereof. The pore size of the porous membrane is large enough to allow ion migration to provide ionicly conductive contact between the anode and cathode, but small enough to prevent direct contact between the anode and cathode or contact due to particle penetration or dendrites that may form on the anode and cathode. Examples of porous membranes suitable for use herein are disclosed in U.S. Application Serial No. 12 / 963,927 (filed December 9, 2010, U.S. Patent Application Publication No. 2012 / 0149852, now U.S. Patent No. 8,518,525), the disclosure of which is incorporated herein by reference in its entirety.

[0237] Many different types of materials are known to serve as cathodes. Suitable examples of cathode materials include, but are not limited to, graphite, graphene, aluminum, platinum, palladium, electroactive transition metal oxides containing lithium or sodium, indium tin oxide, and conductive polymers such as polypyrrole and ferrocene.

[0238] Example cathode active particles include metal oxides, metal sulfides, or lithium metal oxides. In a preferred embodiment, the cathode active particles comprise lithium transition metal oxides. Example lithium metal oxides include: lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LiFePO4), lithium cobalt oxide (LCO), lithium titanate (LTO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the cathode active material may comprise, for example, layered transition metal oxides (such as LiCoO2 (LCO), Li(NiMnCo)O2 (NMC), LiNi 0.8 Co 0.15 Al 0.05 O2 (NCA)), spinel manganese oxides (such as LiMn2O4 (LMO), LiMn 1.5 Ni 0.5 O4 (LMNO) or olivine (such as LiFePO4), LiNiO2, LiNi 1-x Co x O2, LiNi 0.85 Co0.1 Al 0.05 O2, LiNi 0.33 Co 0.33 Mn 0.33 O2, LiMn2O4, and combinations thereof.

[0239] Suitable cathodes include those disclosed in U.S. Patent Nos. 5,962,166, 6,680,145, 6,964,828, 7,026,070, 7,078,128, 7,303,840, 7,381,496, 7,468,223, 7,541,114, 7,718,319, 7,981,544, 8,389,160, 8,394,534, and 8,535,832, and the references therein, the respective disclosures of which are incorporated herein by reference in their entirety. "Rare earth element" refers to the lanthanide elements from La to Lu, as well as Y and Sc.

[0240] In another embodiment, the cathode material is an NMC cathode; that is, a LiNiMnCoO cathode, more specifically, a cathode in which the atomic ratio of Ni:Mn:Co is 1:1:1 (Li a Ni a-b-c Co b R c O 2-d Z d where 0.98 < a < 1.05, 0 < d < 0.05, b = 0.333, c = 0.333, where R contains Mn) or a cathode in which the atomic ratio of Ni:Mn:Co is 5:3:2 (Li a Ni a-b- c Co b R c O 2-d Z d where 0.98 < a < 1.05, 0 < d < 0.05, c = 0.3, b = 0.2, where R contains Mn).

[0241] In another embodiment, the cathode comprises a material of the formula Li a MnbJcO4Zd, where J is Ni, Co, Mn, Cr, Fe, Cu, V, Ti, Zr, Mo, B, Al, Ga, Si, Li, Mg, Ca, Sr, Zn, Sn, a rare earth element, or a combination thereof; Z is F, S, P, or a combination thereof; and 0.9 < a < 1.2, 1.3 < b < 2.2, 0 < c < 0.7, 0 ≤ d < 0.4.

[0242] In another embodiment, the cathode in the electrochemical cell or lithium-ion battery disclosed herein comprises a cathode active material, which, relative to Li / Li "+" The reference electrode exhibits a capacity greater than 30 mAh / g over a potential range greater than 4.6 V. An example of such a cathode is a stable manganese cathode comprising a lithium-containing manganese composite oxide with a spinel structure as the cathode active material. Lithium-containing manganese composite oxides suitable for use herein include those of the formula Li... x Ni y M z Mn 2-y-z O 4-d The oxide, wherein x is 0.03 to 1.0; x varies according to the release and absorption of lithium ions and electrons during charging and discharging; y is 0.3 to 0.6; M includes one or more of Cr, Fe, Co, Li, Al, Ga, Nb, Mo, Ti, Zr, Mg, Zn, V, and Cu; z is 0.01 to 0.18; and d is 0 to 0.3. In one embodiment, in the above formula, y is 0.38 to 0.48, z is 0.03 to 0.12, and d is 0 to 0.1. In one embodiment, in the above formula, M is one or more of Li, Cr, Fe, Co, and Ga. The stable manganese cathode may also comprise a spinel layered composite material containing a manganese-containing spinel component and a lithium-rich layered structure, as described in U.S. Patent No. 7,303,840, which is incorporated herein by reference in its entirety.

[0243] In some embodiments disclosed herein, the reduction in electrochemical reduction occurs by, when used in a secondary lithium-ion battery, in the electrolyte relative to Li / Li ratio during the first reduction scan. + The peak height maximum current in the region of 0.9V to 0.30V is measured as a ratio to the peak height produced in the absence of effective amounts of the following substances: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, (ii) at least one lithium salt additive containing one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide or phosphate groups and optionally fluorine, or (iii) at least one unsaturated C=C bond, excluding VC and VEC, or a combination thereof, wherein the reduction is greater than 80%.

[0244] In some embodiments disclosed herein, the reduction in electrochemical reduction is achieved via a first reduction scan relative to Li / Li +The peak area in the 0.9V to 0.30V region is measured as a ratio to the peak height produced without the additive, wherein the additive comprises at least one lithium salt additive containing one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide groups or phosphate groups, and optionally at least one of the following: (i) a cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1- (ii) C4 alkyl group substitution, and at least one additive containing at least one unsaturated C=C bond, free of VC and / or VEC.

[0245] In some embodiments disclosed herein, the reduction in electrochemical reduction is achieved, preferably when used in a secondary lithium-ion battery, by adjusting the first reduction scan relative to Li / Li. + The peak area in the 0.9V to 0.30V region is measured as the ratio of the peak height produced without the additive, wherein the additive comprises (i) a cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1- C4 alkyl group substitution; and one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding VC and VEC, wherein the reduction is greater than 80%.

[0246] One embodiment of the invention disclosed herein relates to an adhesive comprising a film-coated fibrillated PTFE / TFE-containing polymer and copolymer.

[0247] In some embodiments disclosed herein, the anode comprises, is substantially composed of, or consists of: graphite active anode powder, Super P conductive carbon, a binder containing PTFE or TFE, and a membrane derived from a fluorine component that prevents / reduces binder reduction and extends anode lifetime by scanning between or across a voltage range applied to a LiPF6 solution containing at least two lithium salts selected from: lithium difluorooxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), LiTOP (lithium tri(oxalate)phosphate) and LTFOP (lithium tetrafluoro(oxalate)phosphate), lithium bis(oxalate)difluorophosphate (LIBODFP), lithium bis(fluorosulfonyl)imide (LiFSI), and LiTFSI.

[0248] SEM images of the PTFE binder on the electrodes before and after cycling in the presence of EC / EMC or EC / DEC + 5% FEC electrolyte. Figure 2As shown in (a)-(c), the amount of fibrils in the new electrode in the presence of EC / EMC ( Figure 2 The reduction is greatest after one cycle, and fibrillary instability occurs. This is reduced with the addition of lithium salt lithium fluorocarbonate or lithium borate additives, resulting in the retention of a large number of fibrillary fibers to ensure good adhesion.

[0249] Example

[0250] The disclosed method provides an electrode TFE fluoropolymer used as a binder in the anode of a lithium-ion secondary battery. This fluoropolymer possesses physical properties that provide interparticle fibrillation without initiating fibrillation until the fluoropolymer is homogeneous. This provides fibrillation properties that complement the chemical and physical properties necessary for the anode, most specifically reducing instability, improving coulombic efficiency, and enhancing cycle life.

[0251] The fluoropolymer binder TE-1 used in Examples 1A, 1B, 2A, 2B, Comparative Examples AA, AB, 3A, 3B, DA, and 6A, 7A, 7B, 8A, 8B, 9A, 9B, 10, 11, E, FA, FB, and G is commercially available from Chemours FC LLC, or can be prepared from an aqueous dispersion of a tetrafluoroethylene polymer using known methods. Methods for dispersing fluorinated monomers in aqueous media are known and are prepared using established commercial techniques, such as those taught in U.S. Patent No. 4,576,869 to Malhotra, the disclosure of which is incorporated herein by reference in its entirety.

[0252] Preparation of PTFE binder TE-1

[0253] 600 g of natural paraffin and 4.3 g of succinic acid were charged into a nominal 10-gallon jacketed cylindrical stainless steel reactor with a length-to-diameter ratio of 1.5, equipped with a paddle agitator, and the reactor was sealed. After adding 24.1 L of deionized water, the reactor was heated to 65°C, stirred at 70 RPM, and then pressurized to 400 PSIG with nitrogen and leaks were checked. After purging, an aqueous solution containing 0.7 g of perfluoropolyether acid with a number average molecular weight of approximately 1500 Daltons polymerized from hexafluoropropylene oxide, 147 g of HFPO dimer acid, ammonium salt, and 61.8 g of deionized water was added. The agitator was stopped, the reactor was purged with TFE to greater than 25 PSIG, and evacuated to at least -2.0 PSIG, repeated three times. The agitator was restarted, and TFE was added to the reactor until the pressure reached 400 PSIG. To initiate polymerization, 180 mL of a 0.015% (m / v) potassium permanganate (KMnO4) aqueous solution was added at a rate of 80 mL / min, followed by KMnO4 injection at 3.5 mL / min until 4.7 kg of TFE had been charged from the start of KMnO4 injection. The temperature was raised to 85°C during the charging of the 4.7 kg TFE. After a total of 10.9 kg of TFE had been added since start-up, the TFE addition valve was closed, the stirrer was stopped, and the reactor was slowly vented over 10 minutes. When the reactor pressure reached 1 to 2 PSIG, nitrogen was added to slowly increase the pressure to 5 PSIG. The reactor was evacuated for 1 minute, then the nitrogen flow was stopped, and the reactor was vented. The reaction time was 130 minutes. The resulting dispersion, containing 33.63% polymer, was discharged from the reactor and allowed to cool. The dispersion was found to have an initial particle size of 218.5 nm. After the dispersion was discharged, 495g of condensate containing water, paraffin and polymer was left in the reactor.

[0254] The polymer was coagulated in a 3L container by diluting the dispersion to approximately 14% by weight solids and adding approximately 3.7% by weight (dry weight) of a 20% by weight aqueous solution of ammonium carbonate, followed by vigorous stirring until the polymer was completely separated from the water. The polymer was dried in a static oven at 150°C for 24 hours, yielding 2.1672 SSG.

[0255] Preparation of binder TE-2 with FKM dispersion used in Comparative Example FC and Examples 4A, 5A .

[0256] Preparation of FKM dispersionFKM dispersions were prepared by continuous emulsion polymerization in a well-stirred 2.0-liter stainless steel full-fill reactor at 108°C. An aqueous solution of 6.09 g / h ammonium persulfate, 0.70 g / h sodium sulfite, and 0.91 g / h sodium hydroxide in deionized water was fed into the reactor at a rate of 10 L / h. The reactor was maintained at full level at 6.2 MPa by a back pressure control valve in the effluent line. After 30 minutes, polymerization was initiated by introducing a gaseous monomer mixture consisting of 1547 g / h vinylidene fluoride (VF2) and 11231 g / h hexafluoropropylene (HFP), fed through a diaphragm compressor. After 2.0 hours, the effluent dispersion was collected for 5 hours. The effluent polymer dispersion containing 20% ​​by weight solids was separated from the residual monomers in a degassing vessel at atmospheric pressure.

[0257] The modified tetrafluoroethylene polymer, containing 0.128% by weight of copoly(PPVE) (perfluoro(propyl vinyl ether)) as a modifier, has a strength of 1.47 × 10⁻⁶. 10 Poisson's melt creep viscosity, manufactured by Chemours FC LLC.

[0258] Preparation of binder TE-2: Add 110 mL of softened water, 1643 mL of a dispersion of modified tetrafluoroethylene polymer containing 18.5% polymer solids, 104 mL of an aqueous dispersion of FKM containing 15.69% polymer solids, and 43 mL of a 20% ammonium carbonate solution to a 3-liter glass container equipped with four stainless steel baffles. Complete the assembly by adding a mechanical stirrer equipped with two 4-blade turbine stirrers attached to the central shaft. The dimensions of the complete condenser assembly are as follows: The 3L glass container has an inner diameter of 13 cm. The baffle is connected to a thin metal ring and has a height of 13 cm and a width of 1.5 cm. The two stirrers are spaced 6 cm apart on the shaft and consist of four blades with a 45-degree pitch (blades are 1.5 cm wide and 4.5 cm long). Rotation occurs in the direction that generates an upward flow of fluid. With the lid in place (stirring shaft through the lid), agitate the contents of the coagulator at 800 rpm using a Caframo BDC3030 motor until the solid co-coagulated polymer is fully separated from the water. After decanting, wash the wet powder with 1000 mL of deionized water and then filter through cheesecloth. Dry the powder in a tray oven at 150°C to produce a co-coagulated fluoropolymer composition.

[0259] Electrolyte formulation examples

[0260] Examples 1A, IB: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 1 wt% LiBOB + 4 wt% FEC :

[0261] 0.1579 g of lithium bis(oxalate)borate (LiBOB, Gotion, battery material) and 0.6316 g of fluoroethylene carbonate (FEC, Gotion, battery material) were combined with 15 g of standard electrolyte 1. An electrolyte mixture of 2 M LiPF6 EC / DEC was prepared from Gotion (Fremont, CA) in an inert atmosphere drying oven.

[0262] Examples 2A, 2B: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 10 wt% LiTFSI

[0263] 1.6667 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) (Gotion, battery material) was combined with 15 g of 1.2 M LiPF6 EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0264] Comparative Examples AA, AB: 1.2 M LiPF6+ EC / DEC (3:7 by volume)

[0265] The standard electrolyte containing 1.2 M LiPF6, ethylene carbonate (EC), and diethyl carbonate (DEC) was obtained from Gotion, Freemont, CA.

[0266] Comparative Example FC: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 5 wt% FEC

[0267] 0.7985 g of fluoroethylene carbonate (FEC, Gotion, battery material) was combined with 15 g of 1.2 M LiPF6 EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0268] Comparative Example CA: 1.2 M LiPF6+ EC / DEC (3:7 by volume)

[0269] The standard electrolyte containing 1.2 M LiPF6, ethylene carbonate (EC), and diethyl carbonate (DEC) was used and obtained from Gotion, Freemont CA.

[0270] Example 4A: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 5 wt% LiFSI

[0271] 0.7895 g of lithium bis(fluorosulfonyl)imide (LiFSI) (Gotion, battery material) was combined with 15 g of 1.2 M LiPF6 EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0272] Example 5A: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 5 wt% maleic anhydride

[0273] 0.7895 g of maleic anhydride (Sigma Aldrich, Milwaukee, WI 99.8%) was combined with 15 g of 1.2 M LiPF6 EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0274] Comparative Example DA: 1.2 M LiPF6+ EC / DEC (3:7 by volume)

[0275] The standard electrolyte containing 1.2 M LiPF6, ethylene carbonate (EC), and diethyl carbonate (DEC) was used and obtained from Gotion, Freemont CA.

[0276] Example 6A: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 5 wt% LiTFSI

[0277] 0.7895 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, Gotion, battery material) was combined with 15 g of 1.2 M LiPF6 EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0278] Examples 7A, 7B: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 1 wt% LiDFOB

[0279] 0.7895 g of lithium difluorooxalate borate (LiDFOB, Gotion, battery material) was combined with 15 g of 1.2 M LiPF6 EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0280] Examples 8A, 8B: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 1 wt% LiBOB

[0281] 0.7895 g of lithium bis(oxalate)borate (LiBOB, Gotion, battery material) was combined with 15 g of 1.2 M LiPF6 EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0282] Examples 9A, 9B: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 1 wt% LiDFOB + 4 wt% FEC

[0283] 0.1579 g of lithium difluorooxalate borate (LiDFOB, Gotion, battery material) and 0.6316 g of fluoroethylene carbonate (FEC, Gotion, battery material) were combined with 15 g of 1.2 M LiPF6-EC / DEC, a standard electrolyte obtained from Gotion (Fremont, CA), to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0284] Comparative Example E: 1.2 M LiPF6+ EC / DEC (3:7 by volume)

[0285] The standard electrolyte containing 1.2 M LiPF6, ethylene carbonate (EC), and diethyl carbonate (DEC) was used and obtained from Gotion, Freemont CA.

[0286] Comparative Examples FA, FB: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 5 wt% 1,3 propanesultone

[0287] 0.8001 g of 1,3-propanesulfonate lactone (Gotion battery material) was combined with 14.9987 g of 1.2 M LiPF6 EC / DEC standard electrolyte obtained from Gotion (Fremont, CA) to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0288] Comparative Example G: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 5 wt% succinic anhydride

[0289] 0.7725 g of succinic anhydride (Sigma-Aldrich, St. Louis, MO, 99+% purity) was combined with 15.0390 g of 1.2 M LiPF6 EC / DEC standard electrolyte obtained from Gotion (Fremont, CA) to prepare an electrolyte mixture in an inert atmosphere drying oven.

[0290]

[0291]

[0292]

[0293] Manufacturing and testing procedures for all embodiments

[0294] Anode electrode fabrication

[0295] The test anode was prepared using the fluoropolymer composition of the present invention through the following process:

[0296] Approximately 10 g of mixed powder was produced using 90% graphite (Amsted Graphite Materials, Anmoore, VA), % Super P carbon black, and 5% polymer binder. The graphite and super P carbon black were combined and mixed in a mortar and pestle for approximately 15 minutes.

[0297] The mixture was combined with a fluoropolymer binder into a 250 ml plastic bottle containing approximately ten ZrO2 (10 mm in diameter) grinding media and rolled for about 30 minutes. The powder was then separated from the grinding media.

[0298] A self-standing membrane is produced by placing 3 grams of the mixture onto a small glass mortar and pestle. The material is then manually ground until the powder forms a solid flake. The flake is placed on a Kapton... ® The film is then heated to 100°C on a hot plate. Using a manual steel roller, the film is rolled at 100°C until a uniform film is formed.

[0299] Use a TMAX calender. Before use, heat the calender rolls to 50°C for at least 1 hour. Measure the thickness of the self-standing film before calendering. Set the calender gap to 50 μm to 100 μm below the initial film thickness. For example, if the initial self-standing film thickness is 480 μm, the gap distance is initially set to 400 μm. Place the self-standing film on the rolls. Pass the film through the calender gap twice. At the larger gap distance, the film will detach from the rolls. Hold a sheet of paper under the rolls to capture the film. Decrease the calender gap in 50-micron increments. For each step, pass the film through the calender rolls twice. Eventually, the film will adhere to the rolls, and the film will have passed through the calendering unit in this manner. The calender gap is continuously reduced in 50-micron increments until a final thickness of approximately 100 microns is achieved.

[0300] Battery cell fabrication :

[0301] Electrode disks (12 mm in diameter) are stamped from a self-supporting membrane and dried under vacuum at 120°C for at least 8 hours. A Type 2032 coin cell is assembled using a lithium metal counter electrode, a Celgard 2325 separator, and the electrolyte composition described herein.

[0302] As described above, the anode was prepared by mixing 90% graphite active anode powder, 5% Super P conductive carbon, and 5% PTFE binder using PTFE binder TE-1. Figure 1 The discharge and charge potential curves of a graphite half-cell cell with TE-1 as a binder in EC (CH2O)2C) / EMC (CH3CH2OC(O)OCH3) [Comparative Example AA] and EC / DEC+5% FEC (fluoroethylene carbonate, 4-fluoro-1,3-dioxolane-2-one) electrolyte [Example 3A] are shown for the first cycle. The cell efficiency in EC / DEC+5% FEC is 76.3%, but only 46.3% in EC / EMC electrolyte. Due to the inclusion of FEC in the electrolyte, the efficiency increases by almost 65%.

[0303] Cyclic voltammetry measurements :

[0304] An example of cyclic voltammetry measurements in different electrolyte compositions using a lithium metal half-cell cell assembled as described above within a Bio-Logic potentiostat. Cyclic voltammetry testing preferably includes measurements at a scan rate of 0.05 mV / sec relative to Li / Li + Potential scan from 0V to 1.5V. During the first reduction scan in cyclic voltammetry measurements, relative to Li / Li + Peak height was measured in the potential region from 0.9V to 0.3V. In all cases, the estimated baseline correction was applied to the peak height determination. In the table below, this peak height was divided by the peak height (or average peak area) of the comparative examples in the table. The smaller this ratio, the smaller the reduction current observed in the 0.9V to 0.3V region during cyclic voltammetry measurements.

[0305] Alternatively, during the first reduction scan in cyclic voltammetry measurements, the peak area relative to Li / Li+ in the potential region from 0.9 V to 0.30 V is measured. In this case, integration relies on normalizing the CV dataset relative to a fixed line at the current value present at 0.9 V; that is, subtracting the current value at 0.9 V from the entire dataset before integration. This normalized area under the curve is calculated using five techniques: the Riemann sum with midpoint, right division, and left division, and the trapezoidal sum with uniform and non-uniform divisions. The values ​​from these five techniques are then averaged to obtain the final integrated value. The references describing various integration methods are copied below from Libretexts Mathematics, Section 2.5, Numerical Integration - Midpoint, Trapezoid and Simpson's rule, and incorporated herein by reference, https: / / math.libretexts.org / Courses / Mount_Royal_University / MATH_2200%3A_Calculus_for_Scientists_II / 2%3A_Techniques_of_Integration / 2.5%3A_Numerical_Integration__Midpoint%2C_Trapezoid%2C_Simpson%27s_rule#:~:text=The%20most%20commonly%20used%20techniques,definite%20integral%20using%20trapezoidal%20approximations.

[0306] In the table below, the peak area is divided by the peak area (or average peak area) of the comparative examples in the table. The smaller this ratio, the smaller the reduction current observed in the 0.9V to 0.3V region during cyclic voltammetry measurements.

[0307] Use corresponding Figures 3 to 7 The peak ratios (relative to the reduction peaks of Li / Li+ between 0.9 V and 0.3 V) were determined using cyclic voltammetry data from the scanned examples and are listed in Table 2 below. Numerical integral peak ratios in the 0.9 V to 0.3 V region are also shown.

[0308]

[0309] The data in Table 2 reveal that the use of lithium salt compounds in the electrolyte reduces electrode reduction by at least approximately 40%. In some cases, the reduction is increased by more than 80%. This increase will increase the amount of cyclic lithium in the battery and will also improve the mechanical integrity of the electrodes.

[0310] As shown in the optimal diagram. Figure 3 The cyclic voltammetry methods of Examples 1A, 1B, 2A and 2B are compared with the cyclic voltammetry method of Comparative Example DA; Figure 4 The cyclic voltammetry methods of Examples 6A, 7A, and 7B were compared with the cyclic voltammetry method of Comparative Example DA.

[0311] Figure 5 The cyclic voltammetry methods of Examples 8A, 8B, 9A, and 9B were compared with the cyclic voltammetry method of Comparative Example DA; and

[0312] Figure 6 The cyclic voltammetry of Example 9A was compared with that of Comparative Example DA.

[0313] from Figure 7 The data in Table 3, derived and plotted, reveal that, compared to Comparative Example 3A, the use of a lithium salt compound in the electrolyte and the electrode made with binder TE-2 reduced electrode reduction by at least approximately 40%. In all cases, the estimated baseline correction was applied to the peak height determination.

[0314]

[0315] Comparative Example CA, obtained with an electrode containing TE-2 binder, showed an estimated numerical integral value for the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V in cyclic voltammetry measurements that was very similar to the numerical integral value observed in Comparative Example DA, obtained with an anode containing TE-1 binder. For Comparative Example CA, the integral magnitude of this reduction peak was 0.027, while for Comparative Example DA it was 0.024. In both cases, the electrolyte was 1.2 M LiPF6+ EC / DEC (3:7 by volume), meaning that data from two sets using binders TE-1 and TE-2 can be compared.

[0316] Comparative Example FC shows an electrolyte containing 5 wt% FEC. Here, the numerically integrated reduction peak ratio (measured relative to Li / Li between 0.9 V and 0.3 V) with Comparative Example CA is 0.298. This is the ratio of the integrated reduction peak area to the peak area normalized relative to Comparative Example CA. This value is significantly higher than the values ​​of 0.20 and 0.23 obtained by normalizing the numerically integrated area relative to the reduction peak area of ​​Comparative Example DA observed in Examples 1A and 1B. In this case, an electrolyte containing 1 wt% LiBOB and 4 wt% FEC is used, and this shows a synergistic effect between LiBOB and FEC in reducing the reduction peak amplitude relative to Li / Li+ between 0.9 V and 0.3 V in cyclic voltammetry experiments compared to FEC alone. Similarly, Example 9B shows a synergistic effect between LiDFOB and FEC using a formulation containing 1 wt% LiDFOB and 4 wt% FEC, where the reduction peak amplitude ratio (normalized relative to the integrated peak area of ​​Comparative Example DA) is 0.26.

[0317] Comparative Example: Additive - 1,3-propanesultone / succinic anhydride

[0318] Peak height ratio (relative to Li / Li) was determined using cyclic voltammetry data from comparative examples E, FA, FB, and G. + The reduction peaks are located between 0.9 V and 0.3 V, and are listed in Table 4 below. The data in Table 4 show that the use of 1,3-propanesulfonic acid lactone has an adverse effect on electrode stability, while succinic anhydride has a smaller beneficial effect.

[0319]

[0320] like Figures 3 to 7As shown in the scans, compared to Example DA (Comparative Example), the reduction peak of the graphite electrode formed using the PTFE binder in Examples 1A, 1B, 2A, 9A, and 9B decreased to a value of 0.17. The remaining examples similarly exhibited reduced reduction peaks. As is currently understood, the fluorinated electrolyte additive FEC can decompose / polymerize / react during the first cycle to form a product composed of Li₂CO₃ and LiF on the electrode, as well as PTFE fibrils and graphite. One possible mechanism for FEC polymerization is shown below.

[0321]

[0322] This layer effectively resists polymer instability to prevent further reduction, which has been estimated relative to Li / Li during the first reduction scan in cyclic voltammetry measurements. + The peak height in the potential region from 0.90V to 0.3V is used for semi-quantitative analysis.

[0323] Several mechanisms exist in which the membrane layer is derived from an electrolyte comprising one or more of the following: (i) at least one lithium salt additive containing fluorine and one or more of oxalate, borate, sulfonyl, or sulfonylimide groups; (ii) at least one additive containing at least one unsaturated C=C bond, excluding VC and / or VEC; (iii) at least one fluorinated cyclic additive; or a combination of two or more of (i), (ii), and (iii). These mechanisms include decomposition, incorporation, polymerization (as described herein), copolymerization with other electrolyte components, and copolymerization of partially reduced products from polymers, or combinations thereof.

[0324] Characterization of PTFE degradation by X-ray scattering

[0325] Examples 10 and 11

[0326] After three cycles of cyclic voltammetry testing in an argon glove box, the button cell was disassembled and the anode was removed to collect the X-ray scattered sample. Example 10 was derived from Comparative Example CA, and Example 11 used the electrode of Example 3A, while Example 12 was derived from the original anode used in Examples 10 and 11.

[0327] The samples were sealed with Kapton tape to eliminate any possibility of air exposure. These samples were then fixed in an X-ray scattering instrument and measured under vacuum. Wide-angle X-ray scattering data were collected using a Xenocs (Denmark) Xuess 2.0 combined small-angle scattering / wide-angle scattering instrument. This instrument uses a copper high-throughput source and a multi-panel two-dimensional (2D) detector. Using a 2D detector for current work is extremely important for capturing <5% by weight of PTFE within the electrode, and it is unclear whether the same data fidelity can be captured with a one-dimensional (1D) detector. The samples were scanned for 3 minutes with an electron beam cross-section of 2 mm × 2 nm to generate 2D at a sample-to-detector distance of 72 mm. The Kapton tape used to seal the samples was also scanned under the same conditions. The intensity of the pure Kapton diffraction signal was then scaled to match the amplitude of the Kapton signal within the electrode sample and subtracted from the 2D diffraction pattern via a matrix algorithm. The 2D diffraction signal was then integrated to obtain the 1D diffraction data shown in this patent. All data processing was performed using the XSACT program.

[0328] At this point, the area under the curve corresponding to the main peak of the PTFE binder was taken as a linear approximation, and this value was traced back to the peak height of the original anode (Example 12). The ratio of the post-cycle peak area to the original peak area, given as a percentage, is presented in Table 5 as the PTFE retention value. This data shows that the scattering intensity of PTFE in the system with the FEC additive (Example 11) is twice the peak intensity in the sample without the additive, indicating the significant protective effect of the PTFE binder when the additive is used, and greater retention of the PTFE structure.

[0329]

[0330] Figure 8 The scattering intensity involves the original electrode and the recycled electrode, as well as the graphite and PTFE electrode components. Figure 9 The scattering intensities of VC, MA, and FEC additives are shown.

[0331] Other embodiments

[0332] OE-1. An electrode comprising a polymer on which a film or deposit can be formed, the polymer comprising at least a binder for the electrode, and the electrode comprising, substantially comprising, or comprising the following:

[0333] Materials selected from the following: graphite, graphene, mesophase carbon microspheres (MCMB), silicon, or SiO2. xOr mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composites, lithium-ionized tin oxide, conductive black phosphorus, SnO2, SnO, antimony-containing nanocomposites, aluminum-titanium and molybdenum oxides, and

[0334] The polymer is selected from one of the following: (1) a TFE-free polymer, (2) a TFE-containing fibrillated polymer, (3) a TFE-containing fibrillated copolymer, (4) a fibrillated TFE-containing copolymer, (5) a non-fibrillated TFE-containing polymer, (7) a non-fibrillated TFE-containing copolymer, (8) a non-fibrillated TFE-containing copolymer, or (10) a mixture of the following: (i) a TFE-containing fibrillated polymer, copolymer and copolymer and (ii) a non-fibrillated TFE-containing polymer, a non-fibrillated TFE-containing copolymer and a non-fibrillated TFE copolymer.

[0335] OE-2. An electrode comprising, substantially consisting of, or consisting of the following:

[0336] Materials selected from the following: graphite, mesophase carbon microspheres (MCMB), silicon, or SiO2. x Or mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composites, lithium-ionized tin oxide, conductive black phosphorus, SnO2, SnO, antimony-containing nanocomposites, aluminum-titanium and molybdenum oxides, and

[0337] Polymers selected from one of the following: (1) TFE-free polymers, (2) TFE-containing fibrillated polymers, (3) TFE-containing fibrillated copolymers, and (4) fibrillated TFE-containing co-polymers.

[0338] A membrane or deposit formed by the electrode polymer, electrolyte, and additives, wherein the additives are selected from: (A) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide groups or phosphate groups and optionally fluorine, optionally containing at least one cyclic additive containing a fluorine and a carbonyl group; or (B) a mixture of additives comprising, substantially comprising, or consisting of: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1-The additive is C4 alkyl-substituted and includes one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C=C alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably at least one cyclic additive comprising fluoroethylene carbonate (FEC).

[0339] OE-3. The electrolyte according to OE-1 or OE-2, wherein the additive comprises LiBOB+FEC.

[0340] OE-4. The electrolyte according to OE-1 or OE-2, wherein the additive comprises LiFSI.

[0341] OE-5. The electrolyte according to OE-1 or OE-2, wherein the additive comprises LiFSI+FEC.

[0342] OE-6. The electrolyte according to OE-1 or OE-2, wherein the additive comprises LiDFOB.

[0343] OE-7. An electrolyte according to OE-1 or OE-2, wherein the additive comprises LiBOB.

[0344] OE-8. The electrode according to OE-4, wherein the additive comprises LiDFOB+FEC.

[0345] OE-9. The electrode according to OE-4, wherein the additive comprises LiBOB+FEC.

[0346] OE-10. The electrode according to OE-4, wherein the additive comprises LiFSI.

[0347] OE-11. The electrode according to OE-4, wherein the additive comprises LiFSI+FEC.

[0348] OE-12. The electrode according to OE-4, wherein the additive comprises LiDFOB.

[0349] OE-13. The electrode according to OE-4, wherein the additive comprises LiBOB.

[0350] OE-14. The electrode according to OE-4, wherein the additive comprises LiDFOB+FEC.

[0351] OE-15. An additive according to any one of OE-1 to OE14, wherein each of the additives is present independently in an amount >0.5% by weight to the solubility limit of the additive in the electrolyte, for example in an amount of 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight or higher and all increments and ranges therein.

[0352] OE-16. Any of the above OE embodiments, wherein the electrolyte comprises LiPF6+EC / DEC (3:7 by volume).

[0353] OE-17. In any of the above OE implementations, wherein the at least one unsaturated C=C bond optionally excludes at least one of VEC and VC.

[0354] OE-18. Any of the above OE embodiments, wherein an electrolyte is present, and said electrolyte comprises one of 0.8M, 1.0M, 1.2M or 1.4M LiPF6-EC / DEC solution.

[0355] OE-19. Any of the above OE embodiments, wherein an electrolyte is present, and said electrolyte comprises one or more of the following: lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethyl)tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis(trifluoromethanesulfonyl)imide LiTFSI, lithium perchlorate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate salt, at a concentration of 0.8M, 1.0M, 1.2M, or 1.4M.

[0356] OE-20. An electrolyte comprising one of a 0.8M, 1.0M, 1.2M, or 1.4M solution, said solution comprising one or more of the following: lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethyl)tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis(trifluoromethanesulfonyl)imide LiTFSI, lithium perchlorate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate electrolyte salt; a solvent; and (i) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide groups or phosphate groups and optionally fluorine, and at least one fluorinated cyclic additive, or a mixture of additives, said additive mixture comprising, substantially comprising, or comprising: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein said cyclic additive is unsubstituted or C 1-The additive is C4 alkyl-substituted and includes one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C=C alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably at least one cyclic additive comprising fluoroethylene carbonate (FEC).

[0357] OE-21. An electrolyte comprising one of a 0.8M, 1.0M, 1.2M, or 1.4M solution, said solution comprising one or more of the following: lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethyl)tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium perchlorate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate electrolyte salt; a solvent; and a stabilizing additive selected from: (A) (i) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; (ii) at least one additive containing at least one unsaturated C=C bond; (iii) at least one fluorinated cyclic additive; or a combination of two or more of (i), (ii) and (iii), such as (i) and (ii), (ii) and (iii), (i) and (iii), or (i), (ii) and (iii), provided that the additive containing at least one unsaturated C=C bond (ii) optionally does not include ethylene ethylene carbonate (VEC), ethylene ethylene carbonate (VC), or (B) an additive mixture comprising, substantially comprising, or comprising: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C 1- The additive is C4 alkyl-substituted and includes one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C=C alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably at least one cyclic additive comprising fluoroethylene carbonate (FEC).

[0358] OE-22. A method for preparing any of the above-described electrode embodiments, the method comprising contacting the electrode with an electrolyte selected from 0.8M, 1.0M, 1.2M, or 1.4M, said electrolyte comprising one or more of the following: lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethyl)tetrafluorophosphate (LiPF4(CF3)2), (A) lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium perchlorate, lithium hexafluoroarsenate, or a solution of lithium trifluoromethanesulfonate; and an additive selected from: (i) at least one lithium salt additive comprising oxalate, borate, chlorate, sulfonyl... (i) one or more of a sulfonyl or sulfonyl imide group or a phosphate group and optionally fluorine; (ii) at least one additive containing at least one unsaturated C=C bond; (iii) at least one fluorinated cyclic additive; or a combination of two or more of (i), (ii) and (iii), such as (i) and (ii), (ii) and (iii), (i) and (iii), or (i), (ii) and (iii); or (B) a mixture of additives comprising, substantially consisting of, or consisting of: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C=C bonded. 1- The additive is C4 alkyl-substituted and includes one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene carbonate. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C=C alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably the at least one cyclic additive comprising fluoroethylene carbonate (FEC), and scanned between or across a voltage range selected from 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, or 2.0V to 0.6V, thereby forming one or more reduction-reducing films or deposits on the polymer of the electrode, provided that the additive containing at least one unsaturated C=C bond optionally does not include ethylene ethylene carbonate (VEC) or ethylene ethylene carbonate (VC).

[0359] OE-23. Any method of forming a film is derived from at least one of the following interactions: decomposition, absorption, assimilation, impregnation, incorporation, polymerization, copolymerization with other electrolyte additives and polymer electrode components, copolymerization with a partially reduced polymer of the polymer component of the electrode, or the interaction of at least one of the polymer components or materials of the electrode with an electrolyte composition, said electrolyte composition comprising, in addition to the electrolyte, additives including LiDFOB, LiBOB, LiFSI, LiTFSI, LiDFOB+FEC, LiBOB+FEC, LiFSI+FEC, or LiTFSI+FEC.

[0360] OE-24. A battery comprising: (a) one of a 0.8M, 1.0M, 1.2M, or 1.4M electrolyte composition, said electrolyte composition comprising one or more of lithium hexafluorophosphate (LiPF6), lithium bis(trifluoromethyl)tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium perchlorate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate electrolyte salt, and containing a solvent; (b) One of (A) or (B), wherein (A) comprises at least one lithium salt additive (i), said lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonimide or phosphate groups and optionally fluorine, (ii) at least one additive containing at least one unsaturated C=C bond, (iii) at least one fluorinated cyclic additive, or a combination of two or more of (i), (ii) and (iii), such as (i) and (ii), (ii) and (iii), (i) and (iii), or (i), (ii) and (iii), and (B) comprises an additive mixture comprising, substantially comprising, or comprising: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein said cyclic additive is unsubstituted or C=C bonded. 1- C4 alkyl group substitution, and one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene ethylene carbonate (VEC) and ethylene ethylene carbonate (VC). More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C=C alkyl groups. 1–(c) C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably the at least one cyclic additive comprising fluoroethylene carbonate (FEC), and (c) an anode electrode having an electrochemically derived membrane formed from the polymer components of (a), (b), and (c) in the presence of a scan, the scan being performed between or across a voltage range selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, or 2.0V to 0.6V.

[0361] OE-25. The battery according to OE-24, wherein the electrolyte comprises one of a 0.8M, 1.0M, 1.2M or 1.4M LiPF6-EC / DEC solution, and the additive comprises LiDFOB, LiBOB, LiDFOB+FEC, LiFSI, LiFSI+FEC, LiBOB+FEC, LiFSI or LiDFOB.

[0362] OE-26. In a combination of at least one layer of an electrode and a TFE material in a lithium-ion battery, wherein the film layer is derived from an ion-conducting electrolyte comprising: at least one lithium salt additive comprising one or more of oxalate, borate, sulfonyl or sulfonylimide groups and optionally a fluorine group, and optionally (ii) at least one additive having at least one unsaturated C=C bond, and (iii) at least one fluorinated cyclic additive; or (iv) a mixture of two or more of (i), (ii) and (iii) additives comprising, substantially comprising, or comprise of: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or C=C bonded. 1- C4 alkyl group substitution, and one of the following: (a) at least one lithium salt additive comprising one or more of oxalate, borate, chlorate, sulfonyl or sulfonylimide or phosphate groups and optionally fluorine; and (b) at least one additive containing at least one unsaturated C=C bond, excluding ethylene ethylene carbonate (VEC) and ethylene ethylene carbonate (VC). More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises unsubstituted or C=C alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably at least one cyclic additive comprising fluoroethylene carbonate (FEC).

[0363] OE-27. An electrode that is a component of a secondary lithium-ion battery and exhibits, relative to an electrode without a film layer derived from one of LiDFOB, LiBOB, LiDFOB+FEC, LiFSI, LiFSI+FEC, LiBOB+FEC, LiFSI, LiDFOB, and maleic anhydride in the electrolyte, a Li / Li ratio. + Electrochemical reduction is reduced by 30% between 0.9V and 0.3V, and the electrochemical reduction in the secondary lithium-ion battery is reduced by 40%, 50%, 60% or greater.

[0364] OE-28. An electrode in which the reduction of electrochemical reduction is achieved by, when used in a secondary lithium-ion battery, in a first reduction scan relative to Li / Li + The peak height maximum current in the 0.9V to 0.3V region is measured as a ratio to the peak height generated by LiDFOB, LiBOB, LiDFOB+FEC, LiFSI, LiFSI+FEC, LiBOB+FEC, LiFSI, and LiDFOB in the electrolyte.

[0365] OE-29. The anode according to any OE embodiment disclosed herein, wherein the additive containing at least one unsaturated C=C bond is selected from maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate and does not include VC or VEC.

[0366] OE-30. An electrode wherein the fluorinated cyclic carbonate is selected from fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), trifluoropropylene carbonate (TFPC), 4-((2,2,3,3-tetrafluoropropoxy)methyl)-1,3-dioxolane-2-one (HFEEC) and 4-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dioxolane-2-one (NFPEC), preferably fluoroethylene carbonate (FEC).

[0367] OE-31. Any of the above OEs, including the adhesive polymer selected from one of the following: (1) a TFE-containing polymer that is at least partially fibrillated, (2) a TFE-containing copolymer that is at least partially fibrillated, (3) a TFE-containing co-polymer that is at least partially fibrillated, (4) a mixture of (1), (2) and (3).

[0368] OE-32. Any of the above OEs, including electrode polymers containing fibrillated polymers with TFE.

[0369] OE-33. Any of the above OEs includes electrode polymers containing fibrillated copolymers containing TFE.

[0370] OE-34. Any of the above OEs, including electrode polymers comprising fibrillated TFE co-polymers and electrochemical reduction inhibition films comprising products derived from voltage-initiating mechanisms, said voltage-initiating mechanisms including but not limited to at least one of the following: decomposition, absorption, assimilation, impregnation, incorporation, polymerization, copolymerization with electrolytes, other electrolyte additives and polymer electrode components, or copolymerization with partially reduced polymers of polymer components of electrolyte compositions, said electrolyte compositions comprising 1.2 M LiPF6EC / DEC (3:7 by volume) and one of the following: (1) 1 wt% LiBOB and 4 wt% FEC, (2) 5 wt% to 10 wt% LiFSI, (3) 5 wt% to 10 wt% LiFSI and 4 wt% FEC, (4) 5 wt% LiFSI, (5) 5 wt% LiDFOB, (6) 5 wt% LiBOB or (7) The electrode comprises 1 wt% LiDFOB and 4 wt% FEC, and the electrode comprises, is substantially composed of, or is composed of materials selected from the following: graphite, graphene, mesophase carbon microspheres (MCMB), silicon, or SiO2. x Or mixtures thereof, silicon / carbon / graphite composites, SiO x / carbon / graphite composites, lithium tin oxide, conductive black phosphorus, SnO2, SnO, antimony-containing nanocomposites, aluminum titanium and molybdenum oxides, and polymers selected from the following: (1) a TFE-containing polymer that is at least partially or fully fibrillated, (3) a TFE-containing copolymer that is at least partially or fully fibrillated, (4) a TFE co-polymer that is at least partially or fully fibrillated, or (5) or a mixture of a TFE-containing polymer, copolymer and co-polymer that is at least partially or fully fibrillated.

[0371] OE-35. A method comprising:

[0372] a) Provide electrodes containing conductive components and binder components,

[0373] b) Evaluate the scattering peaks generated by neutrons / X-rays of the component.

[0374] c) Arrange the electrode in a lithium-ion battery containing an electrolyte.

[0375] d) Apply a voltage that scans across the voltage range.

[0376] e) Evaluate the intensity of the scattering peaks produced by neutrons / X-rays in the electrode components described in (d) after the evaluation.

[0377] f) Repeat steps (a)-(d) using a stabilizing additive in the electrolyte, and

[0378] g) Selecting stabilizing additives based on scattering peak intensity

[0379] The stabilizer additive mixture is selected from: at least one lithium salt additive, the lithium salt additive comprising one or more of oxalate, borate, sulfonyl or sulfonylimide groups and optionally fluorine; or at least one additive mixture, the additive mixture containing at least one fluorine-containing cyclic additive.

[0380] OE-36. A method comprising:

[0381] a) Provide electrodes containing conductive components and binder components,

[0382] b) Evaluate the intensity of the neutron / X-ray scattering peaks generated by the electrode components in electrolytes with and without stabilizing additives, and

[0383] c) Select stabilizing additives based on the intensity of the scattering peaks generated by the neutrons / X-rays.

[0384] The stabilizing additive is selected from one of the following: (i) at least one lithium salt additive comprising one or more of oxalate, borate, sulfonyl or sulfonylimide groups and optionally fluorine; or (ii) at least one additive containing at least one unsaturated C=C bond; and at least one fluorinated cyclic additive; or a combination of two or more of (i), (ii) and (iii), provided that (iii) is included.

[0385] OE-37. The electrode according to OE-2, wherein the polymer is reduced or partially reduced.

[0386] OE-38. The electrode according to any one of OE-8 to OE-14, wherein the polymer is reduced or partially reduced.

[0387] OE-39. The membrane according to any one of the above OE embodiments, wherein the membrane may comprise one or more layers, each layer being independently chemically identical or different, and each being independently continuous or discontinuous.

[0388] While certain aspects, embodiments, and principles have been described above, it should be understood that this description is exemplary only and not intended to limit the invention or the appended claims. The various aspects, embodiments, and principles described above can be used individually or in combination with each other.

Claims

1. A self-supporting electrode, the self-supporting electrode comprising: An adhesive having at least partially fibrillated exposed surfaces, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers. At least one binder-electrolyte-derived layer on the exposed surface, the at least one binder-electrolyte-derived layer reducing the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V when using the electrode in cyclic voltammetry measurements at 25 °C, the electrolyte comprising Non-aqueous electrolyte solvents An effective amount of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein said cyclic additive is unsubstituted or C 1- C4 alkyl groups are substituted, and preferably the at least one cyclic additive contains unsubstituted or C4 alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably, the at least one cyclic additive comprises fluoroethylene carbonate (FEC), and At least one additional component selected from the following: (1) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine; and (2) at least one compound containing an unsaturated C=C bond comprising 1-propene 1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, excluding VC and VEC.

2. A self-supporting electrode, the self-supporting electrode comprising: An adhesive having at least partially fibrillated exposed surfaces, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers. At least one binder-electrolyte-derived layer on the exposed surface reduces the amplitude of the reduction peak when using electrodes in cyclic voltammetry measurements at 25°C. Non-aqueous electrolyte solvents An effective amount of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein said cyclic additive is unsubstituted or C 1- C4 alkyl groups are substituted, and preferably the at least one cyclic additive contains unsubstituted or C4 alkyl groups. 1- C2 or C3 fluoroolefin carbonates substituted with C4 alkyl groups, most preferably, the at least one cyclic additive comprises fluoroethylene carbonate (FEC), and The additional components are selected from at least the following: (1) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine; and (2) at least one additive containing unsaturated C=C bonds, comprising 1-propylene 1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free from ethylene carbonate compounds containing VC and VEC. Compared to electrodes lacking the at least one binder-electrolyte-derived layer, the amplitude of the reduction peak of Li / Li+ in cyclic voltammetry measurements was reduced by at least 20% in the range of 0.9 V to 0.3 V.

3. A self-supporting electrode, the self-supporting electrode comprising: An adhesive having at least partially fibrillated exposed surfaces, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers. At least one binder-electrolyte-derived layer on the exposed surface, the at least one binder-electrolyte-derived layer reducing the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V when using an electrode in cyclic voltammetry measurements at 25 °C, the electrolyte comprising: A non-aqueous electrolyte solvent, an effective amount of one of LiTFSI, LIDFOB and LiDFOB, and optionally at least one fluorinated cyclic additive, preferably containing a compound of C2 or C3 fluoroolefin carbonate, most preferably fluoroethylene carbonate (FEC). Compared to electrodes lacking the binder-electrolyte-derived layer, the amplitude of the reduction peak of Li / Li+ in cyclic voltammetry measurements was reduced by at least 20% in the range of 0.9 V to 0.3 V.

4. The electrode according to claim 2 or claim 3, wherein, relative to the electrode without the at least one binder-electrolyte-derived layer, the amplitude of the reduction peak relative to Li / Li+ is reduced by one of 30%, 40%, 50%, 60%, or greater in cyclic voltammetry measurements.

5. The electrode according to claim 1, wherein the electrolyte is substantially composed of a non-aqueous electrolyte solvent, an effective amount of at least one cyclic C2 or C3 fluoroolefin carbonate, and at least one lithium salt, wherein the lithium salt comprises one or more of oxalate, borate, or sulfonyl or sulfonylimide groups and optionally fluorine.

6. The electrode according to claim 2, wherein the electrolyte is substantially composed of a non-aqueous electrolyte solvent, an effective amount of at least one cyclic C2 or C3 fluoroolefin carbonate, and at least one lithium salt, wherein the lithium salt comprises one or more of oxalate, borate, or sulfonyl or sulfonylimide groups and optionally fluorine.

7. The electrode according to claim 1, wherein the fluorinated cyclic carbonate is selected from fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), trifluoropropylene carbonate (TFPC), 4-((2,2,3,3-tetrafluoropropoxy)methyl)-1,3-dioxolane-2-one (HFEEC) and 4-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dioxolane-2-one (NFPEC).

8. The electrode according to claim 3, wherein the fluorinated cyclic carbonate is selected from fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), trifluoropropylene carbonate (TFPC), 4-((2,2,3,3-tetrafluoropropoxy)methyl)-1,3-dioxolane-2-one (HFEEC) and 4-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dioxolane-2-one (NFPEC).

9. The electrode according to claim 1, wherein the fluorinated cyclic carbonate comprises at least fluoroethylene carbonate (FEC).

10. The electrode according to claim 2, wherein the fluorinated cyclic carbonate comprises at least fluoroethylene carbonate (FEC).

11. The electrode of claim 3, wherein the electrolyte comprises LiTFSI.

12. The electrode of claim 3, wherein the electrolyte comprises LiDFOB.

13. The electrode according to any one of claims 12 or 13, wherein the electrode further comprises a cyclic fluorocarbonate selected from the group consisting of fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), propylene trifluorocarbonate (TFPC), 4-((2,2,3,3-tetrafluoropropoxy)methyl)-1,3-dioxolane-2-one (HFEEC) and 4-(2,2,3,3,4,4,5,5,5-nonafluoropentyl)-1,3-dioxolane-2-one (NFPEC).

14. The electrode according to any one of claims 1 to 3, wherein the polymer binder comprises one of the following: A co-condensation composition containing 95% by weight PTFE1 and 10% by weight PFA1. A modified tetrafluoroethylene polymer containing 0.018 wt% copolymer PFBE (perfluorobutylethylene) and 0.016 wt% HFP (hexafluoropropylene) modifier, exhibiting a strength of 1.5 × 10⁻⁶. 11 Poisson's melt creep viscosity A co-condensation composition containing 95% by weight PTFE2 and 5% by weight PFA1. A co-condensation composition containing 95% by weight PTFE2 and 5% by weight PFA1. A co-condensation composition containing >95% by weight of PTFE and up to 5% by weight of FKM. The modified tetrafluoroethylene polymer, containing 0.128% by weight of copoly(PPVE) (perfluoro(propyl vinyl ether)) as a modifier, has a strength of 1.47 × 10⁻⁶. 10 Poisson's melt creep viscosity A co-condensation composition containing 95% by weight PTFE3 and 5% by weight PFA1. A co-condensation composition containing 95% by weight PTFE3 and 10% by weight PFA1. A co-condensed product containing 95% by weight PTFE3 and 5% by weight FKM1, or The modified tetrafluoroethylene polymer, containing 0.038% by weight of copoly(PFBE, perfluorobutylethylene) as a modifier, has a composition of 9.16 × 10⁻⁶. 10 Poisson's melt creep viscosity in PFA1 is a copolymer of tetrafluoroethylene and perfluoro(propyl vinyl ether) (PPVE), with a PPVE content of 4% by weight, a melt flow rate of 15 g / 10 min, and a per 10 6 The content of approximately 200 unstable end groups of total carboxylic acid types per C atom. FKM is a copolymer of vinylidene fluoride and hexafluoropropylene (HFP) with an HFP content of 40% by weight and a Mooney viscosity of 114 MU measured at 121°C. PTFE1 has a melt creep viscosity of 4.0 × 10⁻⁶. 11 Poiseu's tetrafluoroethylene homopolymer, PTFE2 is a modified tetrafluoroethylene polymer containing 0.018% by weight of copolymer PFBE (perfluorobutylene) and 0.016% by weight of HFP (hexafluoropropylene) modifier, and has a strength of 1.5 × 10⁻⁶. 11 Poisson's melt creep viscosity PTFE3 is a modified tetrafluoroethylene polymer containing 0.128% by weight of copoly(PPVE) (perfluoro(propyl vinyl ether)) as a modifier, and has a melt creep viscosity of 1.47 × 10⁻⁶. 10 Po, where “about” is defined as including one of ±1%, ±2% or ±3% up to a specified value.

15. An electrochemical device comprising an electrode according to any one of the preceding claims.

16. A secondary lithium-ion battery, the secondary lithium-ion battery comprising an electrode according to any one of the preceding claims.

17. A battery, the battery comprising: An anode electrode, a cathode, and an electrolyte with a membrane, wherein the anode electrode with the membrane comprises the electrode according to claim 1.

18. A battery, the battery comprising: An anode electrode with a membrane, a cathode, and an electrolyte, wherein the anode electrode with a membrane comprises the electrode according to claim 2.

19. A battery, the battery comprising: An anode electrode, a cathode, and an electrolyte with a membrane, wherein the anode electrode with the membrane comprises the electrode according to claim 3.

20. A method comprising: A binder with at least partial fibrillation and exposed surfaces is provided, said binder being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers. The electrode of (a) is brought into contact with an electrolyte comprising: Non-aqueous electrolyte solvents An effective amount of at least one fluorinated cyclic additive, preferably a cyclic fluorocarbon additive, more preferably a C2 or C3 fluoroolefin carbonate, and most preferably a fluoroethylene carbonate (FEC), and At least one additional component selected from the following: at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine; and at least one compound containing an unsaturated C=C bond, said compound comprising 1-propene-1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free of ethylene carbonate compounds. A scan is applied between or across voltage ranges, and a reduction inhibition film or deposit is formed on the exposed surface of the electrode. When the electrode is used in cyclic voltammetry measurements, the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V is reduced by at least 20% relative to the film formed in the absence of an effective amount of the at least one cyclic fluorocarbonate additive and the at least one additional component.

21. The method of claim 20, wherein, relative to an electrode without the membrane, relative to Li / Li + The amplitude of the reduction peak between 0.9V and 0.3V is reduced by one of 30%, 40%, 50%, 60%, or greater.

22. The method of claim 21, wherein the scan between or across voltage ranges is selected from one of 1.0V to 0.6V, 1.0V to 0V, 1.5V to 0.6V, 1.5V to 0V, or 2.0V to 0.6V relative to Li / Li+.

23. A method for electrochemical reduction of an adhesive for reducing at least partial fibrillation, the adhesive having an exposed surface comprising a copolymer containing PTFE or TFE and a TFE content of at least 90% by weight, the method comprising contacting an electrode formed of the polymer with an electrolyte comprising an effective amount of fluoroethylene carbonate (FEC) and additional components selected from: (1) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine, and (2) at least one compound containing unsaturated C=C bonds comprising 1-propene 1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding ethylene carbonate compounds, wherein the electrode is placed together with a counter electrode in a secondary lithium-ion battery and at least one scan is performed, wherein when a graphite electrode is used, the anode potential is from relative to Li / Li + At least 1.0V or higher relative to Li / Li + At least a 0.6V change, lower limit relative to Li / Li + At 0V, the electrochemical reduction of the polymer and the electrolyte is reduced by at least 20% compared to an electrode having a membrane produced without the combination of FEC and the additional components.

24. The electrode according to any one of claims 20 to 22, wherein the electrochemical reduction of the electrode and the electrolyte in the secondary lithium-ion battery is reduced by 30%, 40%, 50%, 60% or greater.

25. The method according to any one of claims 20 to 22, wherein the reduction in electrochemical reduction is achieved by means of a voltage of 0.9V to 0.3V (relative to Li / Li). + The ratio of the peak height attributable to the reduction in the region to the peak height generated without the combination of FEC and the additional components is measured.

26. The electrode according to any one of claims 1 to 3, wherein the electrode comprises graphite, conductive carbon, and a binder selected from PTFE homopolymer, a TFE copolymer formed with one of hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), FEP, perfluoro(ethyl vinyl ether) (PEVE), or perfluoro(propyl vinyl ether) (PPVE), or a co-condensate, wherein the TFE content is at least 95% by weight.

27. The electrode according to any one of claims 1 to 3, wherein the electrode further comprises silicon, silicon oxide, a combination of silicon and silicon oxide, and graphite.

28. The electrode according to any one of claims 1 to 3, wherein the fibrillated binder having an exposed surface comprises a first polymer and a second polymer, wherein the first polymer is selected from: a fluoropolymer having a different melt creep viscosity than the second polymer, wherein the second polymer is selected from polyolefins, polyesters, polyamides, polyimides, polyaramids, polyacrylates, polyurethanes, polyethers, polyol ethers, polyacrylonitrile, polyphosphazenes, polysiloxanes, polysulfides, and polysulfones.

29. The electrode according to claim 1, wherein the electrolyte composition comprises 1.2 M LiPF6+EC / DEC (3:7 by volume) and one of the following: (a) 1 wt% LiBOB and 4 wt% FEC, (b) 10 wt% LiTFSI, (c) 1 wt% LiFSI and 4 wt% FEC, (d) 5 wt% LiFSI, (e) 1 wt% LiDFOB, (f) 1 wt% LiBOB, or 1 wt% LiDFOB and 4 wt% FEC.

30. The method of claim 2, wherein the electrolyte and electrolyte additive comprise 1.2 M of LiPF6+EC / DEC (3:7 by volume) as the electrolyte and one of the following: (a) 1 wt% LiBOB and 4 wt% FEC, (b) 10 wt% LiTFSI, (c) 1 wt% LiFSI and 4 wt% FEC, (d) 5 wt% LiFSI, (e) 1 wt% LiDFOB, (f) 1 wt% LiBOB, or 1 wt% LiDFOB and 4 wt% FEC.

31. The electrode according to claim 3, wherein the electrolyte composition comprises 1.2 M LiPF6 + EC / DEC (3:7 by volume) and one of the following: (a) 1 wt% LiBOB and 4 wt% FEC, (b) 10 wt% LiTFSI, (c) 1 wt% LiFSI and 4 wt% FEC, (d) 5 wt% LiFSI, (e) 1 wt% LiDFOB, (f) 1 wt% LiBOB, or 1 wt% LiDFOB and 4 wt% FEC.

32. The electrode of claim 14, wherein the electrolyte composition comprises 1.2 M LiPF6+EC / DEC (3:7 by volume) and one of the following: (a) 1 wt% LiBOB and 4 wt% FEC, (b) 10 wt% LiTFSI, (c) 1 wt% LiFSI and 4 wt% FEC, (d) 5 wt% LiFSI, (e) 1 wt% LiDFOB, (f) 1 wt% LiBOB, or 1 wt% LiDFOB and 4 wt% FEC.

33. The method of claim 20, wherein the electrolyte and electrolyte additive comprise 1.2 M of LiPF6+EC / DEC (3:7 by volume) as the electrolyte and one of the following: (a) 1 wt% LiBOB and 4 wt% FEC, (b) 10 wt% LiTFSI, (c) 1 wt% LiFSI and 4 wt% FEC, (d) 5 wt% LiFSI, (e) 1 wt% LiDFOB, (f) 1 wt% LiBOB, or 1 wt% LiDFOB and 4 wt% FEC.

34. The electrode according to claim 4, wherein the electrolyte composition comprises 1.2 M LiPF6+EC / DEC (3:7 by volume) and one of the following: (a) 1 wt% LiBOB and 4 wt% FEC, (b) 10 wt% LiTFSI, (c) 1 wt% LiFSI and 4 wt% FEC, (d) 5 wt% LiFSI, (e) 1 wt% LiDFOB, (f) 1 wt% LiBOB, or 1 wt% LiDFOB and 4 wt% FEC.

35. A method, the method comprising: a. Provide an electrode containing a conductive and at least partially fibrillated TFE binder component, b. Evaluate the scattering peak intensity of electrode components in electrolytes with and without stabilizing additives, and c. Select a stabilizing additive based on the intensity of the scattering peak measured from the electrode.

36. The method of claim 35, wherein the stabilizing additive is selected from an effective amount of at least one cyclic fluorocarbonate additive, preferably a C2 or C3 fluoroolefin carbonate, most preferably fluoroethylene carbonate (FEC), and at least one additional component selected from: (1) at least one lithium salt additive comprising one or more of oxalate, borate, or sulfonyl groups or sulfonylimide and optionally fluorine; and (2) at least one compound containing an unsaturated C=C bond, the compound comprising 1-propylene 1,3-sulcinolone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding ethylene carbonate compounds.

37. The electrode of claim 1, wherein at least one exposed surface layer comprises a plurality of layers, each layer being chemically independent and identical or different, and each layer being independent and continuous, discontinuous, or fragmented.

38. The electrode of claim 2, wherein at least one exposed surface layer comprises a plurality of layers, each layer being chemically independent and identical or different, and each layer being independent and continuous, discontinuous, or fragmented.

39. The electrode of claim 3, wherein at least one exposed surface layer comprises a plurality of layers, each layer being chemically independent and identical or different, and each layer being independent and continuous, discontinuous, or fragmented.

40. The electrode of claim 1, wherein the adhesive surface comprises at least one of the fibrils, nodes, or non-fibrillated components of the adhesive.

41. The electrode of claim 2, wherein the adhesive surface comprises at least one of the surface of the fibrils, nodes, or non-fibrillated components of the adhesive.

42. The electrode of claim 3, wherein the adhesive surface comprises at least one of the surface of the fibrils, nodes, or non-fibrillated components of the adhesive.

43. A self-supporting electrode, the self-supporting electrode comprising: An adhesive having at least partially fibrillated exposed surfaces, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers. At least one binder-electrolyte-derived layer on the exposed surface, the at least one binder-electrolyte-derived layer reducing the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V when using an electrode in cyclic voltammetry measurements at 25 °C, the electrolyte comprising: At least one additive containing unsaturated C=C bonds, said additive comprising 1-propylene 1,3-sulfonolactone, maleic anhydride, 2,5-dihydrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free of ethylene carbonate compounds. Compared to electrodes lacking the at least one binder-electrolyte-derived layer, the reduction peak amplitude of the electrode relative to Li / Li+ was reduced in cyclic voltammetry measurements between 0.9 V and 0.3 V.

44. A self-supporting electrode, the self-supporting electrode comprising: (a) An adhesive having an exposed surface that is at least partially fibrillated, said adhesive being selected from at least one of TFE homopolymers, TFE copolymers, or condensed first TFE copolymers and various second TFE copolymers. (b) At least one binder-electrolyte-derived layer on the exposed surface, the at least one binder-electrolyte-derived layer reducing the amplitude of the reduction peak relative to Li / Li+ between 0.9 V and 0.3 V when using the electrode in cyclic voltammetry measurements at 25 °C, the electrolyte comprising a non-aqueous electrolyte solvent and an effective amount of maleic anhydride. Compared to electrodes lacking the at least one binder-electrolyte-derived layer, the amplitude of the reduction peak of Li / Li+ in cyclic voltammetry measurements was reduced by at least 20% in the range of 0.9 V to 0.3 V.

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