Electrolyte derived films for electrochemically stabilizing electrodes containing fibrillated polymers

Abstract

The present invention relates to electrodes formed with a polymer having stabilizing film(s), methods of providing the stabilizing film(s) and electrolyte compositions which can form the stabilizing film(s).

Description

ELECTROLYTE DERIVED FILMS FOR ELECTROCHEMICALLY STABILIZING ELECTRODES CONTAINING FIBRILLATED POLYMERSCROSS 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 disclosures of which are incorporated herein by reference in its entirety.FIELD

[0002] The present invention relates to electrodes and polymeric components thereof formed from a TFE containing polymer having a film layer derived from the electrolyte, electrolyte additives and the polymeric component, processes of making and using.BACKGROUND

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

[0004] Although polymer binders, including PTFE binders, are electrochemically stable when used in lithium-ion battery cathode electrodes, a PTFE homopolymer is easily reduced when used in an anode electrode due to its electronic structure. If the PTFE homopolymer is used 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 deterioration of PTFE, whicheventually causes electrochemical cycling failure. The electrochemical reduction in PTFE also results in a loss of cell capacity due to the loss of cyclable or reversible lithium, and without wishing to be bound by any theory or explanation, it is believed that the homopolymer will produce LiF along with a reduced or partially or fully defluorinated product.

[0005] Thus, a need exists for a method to stabilize electrodes containing polymer components such as polymeric substrates and binders to prevent the loss of cyclable lithium and to prevent mechanical failure of the electrode during cycling in a lithium ion battery.SUMMARY

[0006] The present invention relates to electrodes for lithium ion batteries (Li B), and more specifically electrodes for use as an anode which includes polymeric components or materials, including but not limited to, polymer substrates, polymeric binders, polymer infrastructure, bearing one or more film layers. The polymeric components are selected from the group comprising, consisting essentially of, or consisting of TFE containing fibrillated polymers, TFE containing copolymers, TFE containing co-coagulated polymers, or mixtures thereof, alone or combined with other polymers or fibrillatable polymers.

[0007] In electrode embodiments disclosed herein one or more layers on a polymer substrate surface, or a reduced polymer substrate surface comprises one or more films independently the same or chemically different, and each independently continuous, non-continuous, fragmented.

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

[0009] In certain embodiments disclosed herein the polymer of the electrode, or polymer upon which the film can form or deposit comprises, consists essentially of, or consist one of: (1 ) fibrillated TFE containing polymers; (2) fibrillated TFE containing copolymers; (3) fibrillated TFE containing co-coagulated polymers; (4) non-fibrillated TFE containing polymers, copolymers, or co-coagulated polymers; or (5) mixtures of one of (i) fibrillated TFE containing polymers, copolymers, and cocoagulated polymers and (ii) non-fibrillated TFE containing polymers, wherein fibrillation can include partial fibrillation.

[0010] In certain embodiments disclosed herein the polymer of the electrode, or polymer upon which the film can form or deposit is optionally free of polyvinylpyrrolidone (PVP).

[0011] In certain embodiments disclosed herein the polymer of the electrode, or polymer upon which the film can form or deposit is a binder for the electrode and comprises, consists essentially of, or consist one of: (1 ) at least partially fibrillated TFE containing polymers;(2) at least partially fibrillated TFE containing copolymers; (4) at least partially fibrillated TFE containing co-coagulated polymers, 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 components or materials of the electrode are derived from at least one of decomposition, absorption, assimilation, infusion, incorporation, polymerization, co-polymerization with other electrolyte additives [ electrolyte solvents and co-solvents ] and polymeric electrode components, co-polymerization with a partially reduced polymer of a polymeric component of the electrode, or combinations of one of the polymeric components or materials of the electrode and the electrolyte compositions which include, in addition to the electrolyte, an additive mixture.

[0013] Certain embodiments disclosed herein relate to additives and mixtures of additives, at suitable levels to be soluble in the electrolyte solvent, and which comprise, consist essentially of, or consist of:(a) at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C1-C4 alkyl group, and one of(1 ) at least one a lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, and(2) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates.

[0014] More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0015] 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 a C1-C4 alkyl group, preferably the at least one cyclic additive comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group.

[0016] Certain preferred embodiments disclosed herein are mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0017] Certain embodiments disclosed herein relate to an additive or mixture of additives at suitable levels to be soluble in the electrolyte solvent, and whichcomprise, consist essentially of, or consist of: at least one of: (i) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, (ii) at least one additive containing at least one unsaturated C=C bond, or (iii) at least one cyclic additive containing fluorine and a carbonyl group, the additive or mixture of additives is selected from one of (i), (i) and (ii), (ii) and (iii), (i) and (iii), or (i), (ii) and (iii), with the proviso that the at least one unsaturated C=C bond optionally excludes vinyl ethylene carbonate (VEC), vinylene carbonate (VC).vinylethylene carbonate (VEC) vinylene carbonate (VC)

[0018] Certain embodiments disclosed herein relate to additives and mixtures of additives at suitable levels to be soluble in the electrolyte solvent, and which comprise, consist essentially of, or consist of:(a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, or(b) mixtures of additives which comprise, consist essentially of, or consist 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 a C1-C4 alkyl group, and (ii) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates.More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstitutedor substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0019] Certain embodiments disclosed herein relate to additives and mixtures of additives, at suitable levels to be soluble in the electrolyte solvent, wherein each of the additives is independently present in an amount of >0.05 wt.% up 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

[0020] In one embodiment of the invention disclosed herein the polymeric component comprises a substrate which can be or can contain a polymer binder. The electrode comprising the substrate can be formed by either wet or dry processes, i.e. , the dry process is performed without a solvent. The polymer(s) of the substrate include, but are not limited to, fibrillated polymers, fluoropolymers, fibrillated fluoropolymers, polymers of PTFE and copolymers of TFE and cocoagulated polymers (homopolymers of PTFE or copolymers of TFE cocoagulated with another polymer) which are at least partially fibrillated. Preferably the polymer comprises fibrillated PTFE homopolymer or a fibrillated TFE containing polymer, TFE containing co-polymer or homopolymers of PTFE or copolymers of TFE containing co-coagulated with another polymer (fluoropolymers having a melt creep viscosity different from that of a second polymer) as described herein. Most preferably the polymer comprises a fibrillated polymer including but not limited to PTFE homopolymer or a TFE containing co-polymer or TFE containing cocoagulated polymer.

[0021] In certain embodiments disclosed herein the voltage for forming the one or more film layers ranges from between 2 V Li / Li+and a voltage not exceeding the decomposition voltage of the polymer; for a PTFE homopolymer this is approximately 0.6 - 0.9 V vs. Li / Li+

[0022] In certain embodiments disclosed herein the polymer of the substrate or a 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.

[0023] In certain embodiments disclosed herein the polymer forming the substrate or component of the electrode comprises, consists essentially of, or consists of one of :(a) polyolefins, polyesters, polyamides, polyimides, polyaramides, polyacrylates, polyurethanes, polyethers, polyolethers, polyacrylonitriles, polyphosphazenes, polysiloxanes, polysulfides and polysulfones,(b) fibrillated TFE containing polymers, fibrillated TFE containing copolymers, non-fibrillated. TFE containing polymers, n on-fibril I ated TFE containing copolymers and mixtures thereof,(c) fibrillated and non-fibrillated co-coagulated fluoropolymers and mixtures thereof, or(d) combinations of (a) and, (b), (a) and (c), (b) and (c), or (a), (b), and (c), or preferably at least partially fibrillated TFE containing polymers, at least partially fibrillated TFE containing copolymers, at least partially fibrillated co-coagulated TFE containing copolymers.

[0024] In embodiments disclosed herein the degree of stabilization of the polymer component, substrate, or polymer binder (preferably containing a fibril structure), in the electrode is monitored by measuring the first reductive peak in the region of 0.9 to 0.3 V versus Li / Li+of a sweep between or across a voltage range while in the presence of an electrolyte composition which includes stabilizing additives selected from one of:(a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, a phosphate group and optionally fluorine and optionally one of (i) at least one additive containing at least one unsaturated C=C bond and / or (ii) at least one cyclic additive containing fluorine, or(b) mixtures of additives, which comprise, consist essentially of, or consist of (i) at least one cyclic additive containing fluorine and at least onecarbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates.More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0025] The measurement can be made galvanostatically or using cyclic voltammetry. In some cases, electrolyte co-solvents such as ethylene carbonate can also possess a reductive peak in the 0.9 V to 0.3 V region as well. A diminution of this reductive peak can also stabilizing with respect to electrochemical reactions of the electrolyte on the electrode surface.

[0026] In certain embodiments disclosed herein the electrolyte compositions comprise, consist essentially of, or consist of:(a) a solvent containing lithium ions,(b) at least one lithium salt additive comprising fluorine and one or more of an oxalate, borate, sulfonyl or sulfonyl imide group, optionally (i) at least one additive containing at least one unsaturated C=C bond excluding VC and VEC and / or (ii) a least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C1-C4 alkyl group, preferably the at least one cyclic additive comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0027] 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, illustrated below:fluoroethylene carbonate (FEC) difluoroethylene carbonate (DFEC)trifluopropylene 4-((2,2,3,3-tetra- 4-(2,2,3,3,4,4,5,5,5- carbonate (TFPC) fluoropropoxy)methyl)-1 ,3- nonafluoropentyl)-1 ,3- dioxolan-2-one (HFEEC) dioxolan-2-on (NFPEC)

[0028] In preferred embodiments disclosed herein mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group 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 a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0029] In certain embodiments disclosed herein the electrolyte composition includes phosphate additives which comprise, consist essentially of, or consist of one or more of: (lithium trix(oxalato) phosphate (LiTOP) and (lithium tetrafluoro(oxalato) phosphate(LiTFOP), and lithium bisoxalatodifluorophosphate (LiBODFP), wherein the phosphate additives can be used alone or in combination with other additives.

[0030] The present invention also relates methods for forming the film layer(s) derived from electrolyte compositions, e.g., the electrolyte containing additives, or possible by interaction of polymer component of the electrode and the electrolyte compositions which contain at least two additives under an applied voltage which, without wishing to be bound by any theory or explanation involves, decomposition, absorption, assimilation, infusion, incorporation, polymerization, co-polymerization with the electrolyte and / or additives, in particular a partially reduced polymer of a polymer electrode substrate or polymeric component of an electrode, or combinations of the above wherein the additives are selected from one of: (i) at least one lithium salt additive comprising fluorine and one or more of an oxalate, borate, sulfonyl or sulfonyl imide group, or phosphate group, and (ii) at least one additive containing at least one unsaturated C=C bond or (iii) at least one cyclic additive containing fluorine), preferably, mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group 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 a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).

[0031] In certain embodiments the electrolyte additives, can associate with (e.g., infuse, absorb, incorporate, imbibe), react, and / or polymerize with other components of the electrolyte to form the film layer(s) on the electrode or a polymeric componentthereof. The film layer can be one or more layers, each of which may be continuous, non-continuous or discontinuous, stabilizes the polymer substrate or polymer component of the electrode from reduction or further reduction. In addition, the film layer can suppress or diminish electrochemical reactions of the electrolyte on the electrode surface.

[0032] In one example, the substrate or polymer component in which reduction is diminished comprises a fibrillated polymer. In accordance with the invention, electrochemical reduction in the first reductive sweep in a secondary lithium ion battery is diminished by at least 20% relative to an electrode lacking the polymer layer derived mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding VC and VEC.

[0033] In some embodiments, electrochemical reduction in the first reductive sweep in a secondary lithium ion battery is diminished by at least 30%, 40%, 50%, 60% or more compared to batteries lacking the inventive additive compositions disclosed herein.

[0034] In certain embodiments disclosed herein the lithium salt additives contain 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 one or more of an oxalate, a borate, a chlorate, a sulfonyl or sulfonyl imide group or a phosphate group.

[0035] In certain embodiments disclosed herein the lithium salt additives, and one or more of C, B, O, N and S atoms, and optionally fluorine, selected from at least one lithium fluoro salt including but not limited to lithium difluoro oxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), lithium bis(trifluoromethanesulfonyl) imide (LiTFSI), (lithium trix(oxalato) phosphate(LiTOP)and LiTFOP (lithium tetrafluoro(oxalato) phosphate), and lithium bisoxalatodifluorophosphate (LiBODFP).

[0036] In certain embodiments disclosed herein the cyclic additive contains fluorine and comprises, consists essentially of, or consists of one of 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).

[0037] In certain embodiments disclosed herein the electrolyte, without limitation comprises, consists or, consists essentially of lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethyl) tetrafluorophosphate (LiPF^CFs)?), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium perchlororate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate.

[0038] In certain embodiments disclosed herein the lithium salt additives containing lithium, optionally fluorine, one or more of C, B, O, Cl, N and S are (is) selected from at least one lithium fluoro lithium salt selected from one of lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), and lithium bis(trifluoromethanesulfonyl)imide (LITFSI) and paired with fluoroethylene carbonate (FEC).

[0039] One embodiment disclosed herein relates to a process of diminishing the magnitude of and / or reducing the magnitude of the reductive peak of an anode of a lithium ion battery, at a voltage of between 0.9 to 0.3 volts versus Li / Li+during the first cycle in cyclic voltammetry.

[0040] Another embodiment disclosed herein relates to dry-processed electrodes comprising a fibrillated binder capable of diminishing the magnitude of and / or reducing reduction and destabilization of the polymer, polymer component, polymer substrate and / or fibrils of an electrode.

[0041] Another embodiment disclosed herein relates to wet processed electrodes comprising a fibrillated binder capable of diminishing the magnitude of and / or reducing reduction and destabilization of the fibrils of an electrode.

[0042] Another embodiment disclosed herein relates to dry-processed electrodes comprising a fibrillated binder having a film formed from lithium salt additives containing lithium, fluorine and one of a carbonate, borate or sulfonyl group in the presence of electrons and lithium ions.

[0043] A still further embodiments relates to diminishing the magnitude of the reductive peak of an electrode between 0.9 to 0.3 volts versus Li / Li+by at least one of 30%, 40%, 50% or 60%.

[0044] A still further embodiment relates to diminishing the magnitude of the reductive peak by at least one of 40%, 50% or 60% of an electrode at between 0.9 to 0.3 volts of a cycle through the formation of a film comprising, e.g., through decomposition / polymerization / reaction products of a cyclic carbonate

[0045] A still further embodiment relates to diminishing the magnitude of and / or reducing the magnitude of the reductive peak by at least one of 40%, 50% or 60% of an electrode at between 0.9 to 0.3 volts of a reductive sweep through the in situ formation of one or more film layers by polymerization, optionally in the presence of other electrolyte components or with the reduced polymer substrate or decomposition or incorporation of lithium salt additives containing lithium, fluorine and one of a carbonate, borate or sulfonyl group.

[0046] A still further embodiments relates to diminishing the magnitude of the reductive peak of an electrode between 0.9 to 0.3 volts versus Li / Li+by at least one of 40%, 50% or 60% by forming an electrode film from an electrolyte solution which comprises, consists essentially of, or consists of LiPFe containing electrolyte, linear and / or cyclic carbonates, fluorinated solvents, and at least one of lithium fluoro lithium salt selected from one of lithium difluoro oxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and fluoroethylene carbonate (FEC).

[0047] Another embodiment disclosed herein relates to a composition and method which reduces, prevents, or minimizes the magnitude of the reductive peak of a dry-processed electrodes formed with fibrillating binders by providing and / or forming film layer(s), wherein the electrolyte contains at least one unsaturated C2-C4 carbonate solvent, excluding VC or VEC, and at least one lithium salt additiveselected from the lithium salt compound containing fluorine and one of a carbonate, borate or sulfonyl group which can undergo polymerization, co-polymerization, with other electrolyte components, decomposition / polymerization / reaction products, or associated with or incorporated into a film on an electrode containing a polymer which optionally includes a fibril infrastructure or network

[0048] One embodiment disclosed herein relates to an additive composition which comprises, consists essentially of, or consists of at least one lithium salt compound containing one of a carbonate, borate, or sulfonyl group which can be used to derive a film on an electrode preferably containing a fibrillated infrastructure, wherein the amount of the additive composition is between 1 and 10 wt.% based on the total amount of an electrolyte solution and the additive composition, wherein the electrolyte solution preferably comprises, consists essentially of, or consists of LiPFe in a solvent, wherein the solvent or a solvent mixture for an electrolyte composition that can comprise, consist essentially of, or consist of, without limitation, linear carbonates such as diethyl carbonate, ethyl methyl carbonate, or dimethyl carbonate, cyclic carbonates such as ethylene carbonate, and fluorinated carbonates, esters, or ethers or their combination, except for VEC and VC.Additionally, fluorinated and non-fluorinated solvents can be used, for example, nonfluorinated ethers such as the cyclic ether tetrahydrofuran, and fluorinated solvents such as 2,2 difluoroethyl acetate, a fluorinated ester, or 2,2 difluoroethyl methyl carbonate, a fluorinated carbonate. In all cases, the electrolyte can comprise more than one solvent, and in many cases, two or more solvents. One preferred mixture comprises, consists essentially of, or consists of an EC / DEC mixture or blend.

[0049] Another embodiment disclosed herein relates to an electrolyte which comprises, consists essentially of, or consists of an electrolyte solution of LiPFe, ethylene (EC) and diethylene carbonate (DEC), and at least one additive selected from one or more of a lithium salt fluorinated additive selected from of lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI); fluoroethylene carbonate (FEC); maleic anhydride; and1 -propene 1 ,3 sultone.

[0050] Another embodiment disclosed herein relates to an electrolyte which comprises, consists essentially of, or consists of an electrolyte solution of LiPFe, ECand DEC, and at least one of lithium difluoro oxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and fluoroethylene carbonate (FEC).

[0051] Another embodiment disclosed herein relates to an electrolyte which comprises, consists essentially of, or consists of solvated LiPFe in EC / DEC in a v / v ratio of 2-5:5-8, 1 A to 2:3 by volume, 1 :4 to 5:8, preferably 3:7 by volume, and a fluoroethylene carbonate (FEC) additive paired with at least one of lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) additive, wherein the respective amount of electrolyte additives is between 0.05 wt. %, >0.1 wt %, 0.5 wt.%, 1 wt.%, 2 wt. %, 3 wt.%, 4 wt.%, 5 wt. % up to the solubility limit of the respective additive in the electrolyte which can be greater than 5 wt.%, e.g., 6 wt. %, 7 wt.%, 8 wt.%, or 9 wt. %, or up to an including 10 wt.%, 20wt.% or 30wt.%.

[0052] In other embodiment disclosed herein the total amount or upper limits of additives included in the electrolyte is limited by additive solubility in the electrolyte.

[0053] Another embodiment disclosed herein relates to an electrolyte which comprises, consists essentially of or consists of an electrolyte solution of LiPFe, EC, DEC, and the additives fluoroethylene carbonate (FEC) and a lithium boron oxalate.

[0054] Another embodiment disclosed herein relates to an electrolyte which comprises, consists essentially of, or consists of an LiPFe electrolyte solution and lithium fluorosulfonyl imide as an additive.

[0055] Another embodiment disclosed herein relates to an electrolyte solution which comprises, consists essentially of, or consists of an LiPFe electrolyte solution, a decomposition additive precursor comprising fluoroethylene carbonate (FEC) and a lithium fluorosulfonyl imide.

[0056] Another embodiment disclosed herein relates to a process of reducing the reductive peak of an electrode over a voltage range including, but not limited to, between 0.9 to 0.3 volts versus Li / Li+, wherein the electrode comprises, consists essentially of, or consists of one or more materials selected from silicon, SiOx, lithium alloys such as lithium - aluminum alloy, lithium - lead alloy, lithium - silicon alloy, andlithium - tin alloy ; carbon materials such as graphite, graphene, carbon nanotubes, mesocarbon microbeads (MCMB ) carbon nanotubes, conductive carbon,; phosphorus -containing materials such as. conductive black phosphorus, metal oxides such as SnC>2, SnO and TiO?; nanocomposites containing antimony or tin, for example nanocomposites containing antimony, oxides of aluminum, titanium, or molybdenum(See Chem . Mater. 21 , 3898-3904, 2009) the disclosure of which is incorporated herein by reference in its entirety) and a polymer, preferably a polymer binder optionally having a fibrillated structure comprising: contacting the electrode formed with the polymer (or binder) and an electrolyte comprising (i) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide 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 cyclic carbonyl additive containing fluorine, wherein the additive(s) is (are) selected from (i), (i) and (ii), (i) and (iii), (ii) and (iii), or (i), (ii) and (iii), wherein the electrode is placed in a secondary lithium ion battery with a counter electrode and at least one sweep is performed where the anode potential is varied from at least 2.0 V vs. Li / Li+or higher and should have a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.5 to 0.07, or about 0.6 to about-0.9 V vs. Li / Li+, where the electrochemical reduction of the polymer and the electrolyte is diminished by at least 20% relative to a film produced without the above additive mixture.

[0057] Another embodiment disclosed herein relates to dry electrodes which comprise, consist essentially of or consist of one of graphite, graphene, conductive carbon, metal oxides, SiOxand a fluoropolymer binder, optionally having an exposed fibril structure having a surface is covered, e.g., fully, partially, by a decomposition I polymerization I reaction component product formed from an additive mixture of at least one fluorinated lithium salt, e.g., carbonate, borate, or sulfonylimide, preferably at least one of lithium difluoro oxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), and maleic anhydride in the presence of a 0.8 M, 1 .0 M, 1 .2 M, or 1 .4 M LiPFs-EC / DEC solution, and optionally fluoroethylene carbonate (FEC).

[0058] Another embodiment disclosed herein relates to dry electrodes comprises, consists essentially of or consists of graphite, graphene, conductive carbon, and a fibrillated fluoropolymer binder, wherein an exposed fibril / node / binder / electrode surface is covered by a component product comprising at least two of (a) a lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), and maleic anhydride, and (b) fluoroethylene carbonate (FEC).

[0059] Another embodiment disclosed herein relates to dry electrodes comprises, consists essentially of or consists of graphite, graphene, conductive carbon, and at least a partially fibrillated fluoropolymer binder, wherein an exposed fibril / node surface is covered by a polymer film derived from a decomposed / polymerized / reaction component of a LiPFe solution containing at least two of lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), LiTFSI, and fluoroethylene carbonate (FEC).

[0060] One embodiment disclosed herein relates to a process of forming an electrode by contacting a surface of a graphite electrode containing a fibrillated binder with a LiPFe-EC / DEC solution containing at least two of lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), or LiTSI, and fluoroethylene carbonate (FEC), and applying a sweep between or across a voltage range selected from one of 1.0 V to 0.6 V, 1 .0 V to 0 V, 1 .5 V to 0.6V, 1.5 V to 0 V, 2.0V to 0.6V, 2.0 V to 0 V, or 2.0V to lower limit potential which is more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6-0.9 V vs. Li / Li+.

[0061] One embodiment disclosed herein relates to a process of forming a layer on an electrode by contacting a surface of a graphite electrode containing a fibrillated binder with decomposed / polymerized / reaction component of fluorinated lithium salts and LiPFs-EC / DEC in the presence of sweep across a voltage selected from one of 1.0 V to 0.6 V, 1 .0 V to 0 V, 1 .5 V to 0.6V, 1.5 V to 0 V, 2.0V to 0.6V, or 2.0 V to 0 V, or 2.0 V to a lower limit having a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+.

[0062] In certain embodiment disclosed herein the fibrillated binder is a fluoropolymer, such as PTFE and TFE containing copolymers, preferably wherein the binder comprises, consists essentially of, or consists of PTFE, or TFE copolymers formed with one of hexafluoropropylene (HFP), and / or perfluoro(alkyl vinyl ether) (PAVE) in which the linear 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 the combination of perfluoro(m ethyl vinyl ether)(PMVE) and PPVE, i.e. TFE / PMVE / PPVE copolymer (MFA).

[0063] One embodiment disclosed herein relates to an electrode comprising a fibrillated binder, e.g., a binder including a fibrillated PTFE or TFE-copolymer, and a layer formed in the presence of a sweep across a voltage selected from one of 1.0 V to 0.6 V, 1.0 V to 0 V, 1 .5 V to 0.6V, 1 .5 V to 0 V, 2.0V to 0.6V or 2.0 V to 0 V, or a sweep across a voltage lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+and at least one fluorinated lithium salt additive preferably as defined herein (or a sweep across a voltage lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is between 0.5 and 0.7, preferably about 0.6 - 0.9 V vs. Li / Li+), wherein “about” is defined to include one of ± 1 %, ± 2%, or ± 3% of 0.6 V, 0.7 volts, 08 volts or 0.9 volts.

[0064] Another embodiment disclosed herein relates to process which comprises, consists essentially of, or consists of applying at least a single sweep across a voltage selected from one of 1 .0 V to 0.6 V, 1.0 V to 0 V, 1.5 V to 0.6V, 1 .5 V to 0 V, 2.0V to 0.6V or 2.0 V to 0 V (or a sweep across a voltage lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+) to dry-processed graphite electrode comprising a polymer binder that is in contact with a LiPFs solution containing at least two fluorinated lithium salt additives selected from lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate) borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI) or LiTFSI, and optionally fluoroethylene carbonate (FEC).

[0065] Another embodiment disclosed herein relates to a dry-processed graphite electrode comprising a fibrillated binder having a layer, wherein the electrode is placed in a secondary lithium ion battery and at least one sweep across a voltage is performed where the anode potential is varied from at least 2.0 V vs. Li / Li+or higher to at least 0 V (or a sweep between or across a voltage range lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is between 0.5 and 0.7, preferably about 0.6 - 0.9 V vs. Li / Li+) vs Li / Li+, and the electrolyte contains at least one fluorinated additive, wherein “about” is defined to include one of ± 1%, ± 2%, or ± 3% of 0.6 V, 0.7 V, 0.8 V, or 0.9 resulting in the layer.

[0066] Another embodiment disclosed herein relates to graphite electrodes comprising a binder wherein the electrode is placed in a secondary lithium ion battery and at least one sweep across a voltage is performed where the anode potential is varied from at least 2.0 V vs. Li / Li+or higher to at least 0 V (or a sweep across a voltage lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is between 0.5 and 0.7 V, preferably about 0.6 -0.9 V vs. Li / Li+) vs Li / Li+, and the electrolyte contains at least one fluorinated lithium salt additive, , wherein “about” is defined to include one of ± 1 %, ± 2%, or ± 3% of 0.6 V, 0.7 V, 0.8 V, or 0.9 V.

[0067] Another embodiment disclosed herein relates to a dry-processed graphite electrode comprising a fibrillated binder having a destabilization resistive layer formed in the presence of a sweep across a voltage selected from one of 1 .0 V to 0.6 V, 1 .0 V to 0 V, 1 .5 V to 0.6V, 1 .5 V to 0 V, 2.0V to 0.6V or 2.0 V to 0 V and at least fluorinated additive, and between 0.9 to 0.3 volts of a first sweep reduction peak of an electrode is minimized or reduced by at least 40%, 50% or 60%.

[0068] Another embodiment relates to processes for forming film layer(s) onto an anode electrode containing a fibrillated polymer in a secondary lithium ion battery with an electrolyte comprising (i) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide 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 cyclic additive containing fluorine, or acombination of (i) and (ii), (ii) and (iii) or (i) and (iii), wherein the electrode is placed in a secondary lithium ion battery and at least one sweep is performed where the anode potential is varied from at least 2.0 V vs. Li / Li+or higher to at least 0 V vs Li / Li+(or a sweep across a voltage lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+).

[0069] In certain embodiments disclosed herein at a voltage between 0.9 to 0.3 volts of a reverse cycle, the reduction peak of an electrode comprising a PTFE or TFE-copolymer binder in a lithium electrolyte is reduced or decreased by between 40% and 70%.

[0070] One embodiment of the invention disclosed herein relates to a binder which comprises fibrillated PTFE containing polymers.

[0071] In certain embodiment disclosed herein a fluoropolymer binder of the electrode comprises, consists essentially or, or consists of PTFE that has been or can be fibrillated.

[0072] In certain embodiments disclosed herein the anode comprises, consists essentially of, or consists of graphite active anode powder, Super P conductive carbon, a PTFE or TFE containing binder, and a decomposed / polymerized / reaction component product or polymerized layer with prevents / reduces reduction of the binder, and prolongs the life of the anode formed by a sweep across a voltage applied to a LiPFe solution containing at least two of lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB) lithium bi(fluorosulfonyl) imide (LiFSI), or LiTFSI, and fluoroethylene carbonate (FEC), preferably lithium salts or lithium salts and FEC.

[0073] In certain embodiments disclosed herein an electrode includes a polymer upon which a film layer or deposit can form, the polymer comprises at least a binder for the electrode, and the electrode comprises, consists essentially of, or consist of:(a) a material selected from graphite, graphene, mesocarbon microbeads (MCMB ), silicon, or SiOx or mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composite, lithiated tin oxide,conductive black phosphorus, SnC>2, SnO, nanocomposites containing antimony, oxides of aluminum titanium and molybdenum, and(b) a polymer selected from one of: (1 ) fibri Hated TFE containing polymers, (2) fibrillated TFE containing copolymers, (3) fibrillated TFE containing co-coagulated polymers, (4) at least partiality fibrillated TFE containing co-coagulated polymers, or (5) mixtures of one of fibrillated TFE containing polymers, copolymers, and co-coagulated polymers, and non-fibrillated. TFE containing polymers, non-fibrillated TFE containing copolymers, and non-fibrillated TFE co-coagulated polymers.

[0074] In certain embodiments disclosed herein an electrode includes a polymer, a film layer or deposit, the polymer comprises at least a binder for the electrode, and the electrode comprises, consists essentially of, or consist of: (a) a material selected from graphite, graphene, mesocarbon microbeads (MCMB ), silicon, or SiOx or mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composite, lithiated tin oxide, conductive black phosphorus, SnO2, SnO, nanocomposites containing antimony, oxides of aluminum titanium and molybdenum, (b) a polymer selected from one of: fibrillated TFE polymers, fibrillated TFE containing copolymers, fibrillated TFE co-coagulated polymers, non-fibrillated TFE containing polymers, copolymers, wherein fibrillation is partial or complete, and (c) an electrochemically derived and / or initiated film formed from the electrode polymer, an electrolyte, and (A)- at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, optionally at least one additive (containing one of at least one unsaturated C=C bond excluding VC or VEC, and at least one cyclic additive containing fluorine, or (B), preferably (B) is an additive mixture which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding VC and VEC.

[0075] 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 belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 illustrates the discharge and charge potential profiles of the 1stcycle of the graphite half cells with TE-1 as binder in EC / EMC and EC / DEC+5% FEC electrolytes.

[0077] Figure 2 compares SEM scans of fresh and cycled electrodes.

[0078] Figure 3 illustrates a first comparative voltammetry scan.

[0079] Figure 4 illustrates a second comparative voltammetry scan.

[0080] Figure 5 illustrates a third comparative voltammetry scan.

[0081] Figure 6 illustrates a fourth comparative voltammetry scan.

[0082] Figure 7 illustrates a fifth comparative voltammetry scan.

[0083] Figure 8 illustrates baseline x-ray diffraction scans for electrode components.

[0084] Figure 9 illustrates comparative x-ray diffraction scans for electrolyte additives.DETAILED DESCRIPTION

[0085] The present invention relates to electrodes fabricated with a polymer binder in which at least the fibrils of the binder are protected again destabilization, methods of preparing and compositions therefor.

[0086] More specifically, the present invention relates to films derived from an electrolyte solution containing lithium salt additives that are fluorinated, and contain one or more of C, B, O, N and S atoms, can undergo decomposition I polymerization / reaction during cyclic voltammetry and interact by one or more of, e.g., decomposition, absorption, assimilation, infusion, incorporation, polymerization, co-polymerization with other electrolyte additives and components, co-polymerization with a partially reduced polymer of a polymer substrate or polymeric component of an electrode, or combinations of the above to form a film which diminishes the magnitude of the reductive peak during cyclic voltammetry, to minimize or prevent destabilization of the electrode and binder and stabilize the electrolyte from reduction on the electrode surfaces

[0087] In electrode embodiments disclosed herein the one or more layers on a polymer substrate surface, or a reduced polymer substrate surface comprises one or more films independently the same or chemically different , and each independently continuous, non-continuous, fragmented.

[0088] Before addressing details of embodiments described herein, some terms are defined or clarified as follows.

[0089] The term “ electrolyte composition " as used herein, refers to a chemical composition that includes at a minimum a solvent for an electrolyte salt and an electrolyte salt, wherein the composition is suitable as an electrolyte in an electrochemical cell. An electrolyte composition can include other components to enhance the performance of the battery in safety, reliability, and or efficiency.

[0090] The term “ electrolyte salt ” as used herein, refers to an ionic salt that is at least partially soluble in the solvent of the electrolyte composition and that at least partially dissociates into ions in the solvent of the electrolyte composition to form an ionically conductive electrolyte composition.

[0091] An “ electrolyte solvent” as defined herein is a solvent or a solvent mixture for an electrolyte composition that can comprise, for example and without limitation, linear carbonates such as diethyl carbonate, ethyl methyl carbonate, or dimethyl carbonate, cyclic carbonates such as ethylene carbonate, and fluorinated carbonates, esters, or ethers or their combination. Additionally, fluorinated and non-fluorinated solvents can be used, for example, non-fluorinated ethers such as the cyclic ether tetrahydrofuran, and fluorinated solvents such as 2,2 difluoroethyl acetate, a fluorinated ester, or 2,2 difluoroethyl methyl carbonate, a fluorinated carbonate. In all cases, the electrolyte can comprise more than one solvent, and in many cases, two or more solvents.

[0092] The term " anode” refers to the electrode of an electrochemical cell. In a secondary ( i.e. rechargeable ) battery. The anode is the electrode at which oxidation occurs during discharge and reduction occurs during charging.

[0093] The term " cathode” refers to the electrode of an electrochemical cell. In a secondary ( i.e. rechargeable ) battery. The cathode is the electrode at which reduction occurs during discharge and oxidation occurs during charging.

[0094] The term “ lithium ion battery ’’refers to a type of rechargeable battery in which lithium ions move from the anode to the cathode during discharge and from the cathode to the anode during charge.

[0095] As used herein the terms product, film, layer or deposit “derived from” and “generated from” is meant to include, without wishing to be bound by any theory or explanation, products, films, layers or deposits formed from, inter alia, decomposition, absorption, assimilation, infusion, incorporation, polymerization, reaction, co-polymerization with other electrolyte additives and components, copolymerization with a partially reduced polymer of a polymer substrate or polymeric component of an electrode, or combinations of the above.

[0096] The “derived” / ”generated” product, film, layer or deposit is one or more continuous or discontinuous films / layers on the polymer / binder which may be different than another layer on other electrode components. The derived / generated product, film, layer or deposit may comprise one or more layers or films, wherein each layer or film of a multiple layer or film is independently continuous or discontinuous. The polymer substrate or the polymeric component of the electrode optionally includes a structure comprising one of fibrils and node.

[0097] As used herein, fluoroelastomers include, but are not limited, to repeating units arising from two or more types of monomers and optionally have cure sitesallowing for crosslinking to form a three dimensional network. A first monomer type gives rise to straight fluoroelastomer chain segments with a tendency to crystallize. A second monomer type having a bulky group is incorporated in to the fluoroelastomer chain at intervals to break up such crystallization tendency and produce a substantially amorphous elastomer. Monomers of utility for straight chain segments are those without bulky substituents and include, but are not limited to, vinylidene fluoride (VDF); CH2=CF2:tetrafluoroethylene (TFE), CF2=CF2: chlorotrifluoroethylene (CTFE), CF2=CFCI; and, ethylene (E), CH2=CH2. Monomers with bulky groups useful for disrupting crystallinity include hexafluoropropylene (HFP), CF2=CFCF3; 1 - hydropentafluoropropylene, CHF^CFCFs; 2-hydropentafluoropropylene, CF2=CHCFS; perfluoro(alkyl vinyl ether)s (e.g., perfluoro(methyl vinyl)ether (PMVE), CF2=CFOCF3); and propylene (P), CH2=CHCH3, as disclosed in commonly owned U.S. Patent Publication 2011 / 0200826A1 , incorporated herein by reference in its entirety. See also, Fluoroelastomers are generally described by A. Moore in Fluoroelastomers Handbook: The Definitive User's Guide and Databook, William Andrew Publishing, ISBN 0-8155-1517-0 (2006). incorporated herein by reference in its entirety.

[0098] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B is true (or present).

[0099] The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0100] The transitional phrase “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term ‘consisting essentially of’ occupies a middle ground between “comprising” and ‘consisting of.’

[0101] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of.”

[0102] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0103] Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. Moreover, all ranges set forth herein are intended to include not only the particular ranges specifically described, but also any combination of values therein, including the minimum and maximum values recited.

[0104] When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed.

[0105] Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0106] As used herein, the equilibrium potential between lithium and lithium ion is the potential of a reference electrode using lithium metal in contact with the non - aqueous electrolyte containing lithium salt at a concentration sufficient to give about 1 mole / liter of lithium ion concentration, and subjected to sufficiently small currents so that the potential of the reference electrode is not significantly altered from its equilibrium value (Li / Li+). The potential of such a Li / Li+reference is assigned here the value of 0.0 V .

[0107] As used herein “voltage” means the voltage difference between the cathode and the anode of a full cell, neither electrode of which may be operating at a potential of 0.0 V versus Li / Li+. In a half cell, lithium metal is used as a counter electrode, so the counter electrode is at 0.0 versus Li / Li+.

[0108] As used herein the term “about” in certain embodiments can be quantified to mean ± 1%, ± 2%, ± 3% up to and including ±10% of the stated value, and all whole numbers and fractions therebetween.

[0109] As used herein the term “cyclic voltammetry” is meant to mean the principle of linear sweep voltammetry across a voltage potential that is a technique to measure the current while the potential is swept is generally linear as a function of time. In a cyclic voltammetry measurement, the sweep across the voltage potential is reversed.

[0110] As used herein the term “reductive cycle is meant to mean the first linear sweep in a cyclic voltammetry measurement from positive to negative potentials, or in a galvanostatic measurement from positive to negative potentials in a lithium ion battery.

[0111] As used herein the term “peak amplitude” is meant to mean the maximum peak current in observed due to e.g., decomposition, or more specifically, reduction of the polymer.

[0112] As used herein the term “sweep”’ is intended to mean “ the voltage between or across a voltage range between two values, yielding two current vs. voltage curves with hysteresis.

[0113] As used herein the term “fibrillated” is meant to mean that the polymer is capable of forming nanosized (in at least one dimension (i.e., <100 nm width) fibrils which can vary in length from submicrometer, to several, to tens of micrometers in length when the polymer / copolymer, e.g., is subjected to shear forces.

[0114] As used herein the term “PTFE or TFE based, i.e., contains TFE,” binder is meant to mean a PTFE homopolymer formed from polymerizing tetrafluoroethylene monomers, or a TFE containing copolymer contains tetrafluoroethylene (TFE) co-polymerized with other monomers.

[0115] In certain embodiments disclosed herein electrolyte salts include without limitation lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethyl) tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium perchlororate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate.

[0116] In certain embodiments disclosed herein lithium salt additives, include, but are not limited to phosphorus containing compounds, such as LiTOP (lithium tri(oxalato) phosphate). LiTFOP (lithium tetrafluoro(oxalato) phosphate) and, lithium bisoxalatodifluorophosphate (LiBODFP).

[0117] In certain embodiments disclosed herein electrolyte salt may be present in the electrolyte composition is selected from one of 0.2 M to 2.0 M, including but not limited to about 0.3 M to about 1.7 M, from about 0.5 M to about 1.2 M, or from about 0.5 M to about 1 .7 M.

[0118] One concept of the present invention is to provide a lithium battery with a graphite-carbon electrode containing a PTFE or TFE containing binder that is resistant to, or resistive of destabilization of the fibrillated binder to substantially maintain the integrity of the fibril structure, binder and electrode.

[0119] In one embodiment, the binder comprises a tetrafluoroethylene homopolymer, consisting essentially of repeating units arising from the tetrafluoroethylene monomer, as disclosed in U.S. Provisional Application No. 63 / 411 ,777, filed September 30, 2022, now International Application No. WO 2024 / 072861, published April 4, 2024 , entitled, “ DRY FRIABLE FLUOROPOLYMER AGGLOMERATE COMPOSITIONS FOR USE AS BINDER IN LITHIUM-ION SECONDARY BATTERY ELECTRODES”, the disclosure of which is incorporated herein by reference in its entirety.

[0120] In another embodiment the tetrafluoroethylene polymer is a “modified” PTFE, referring to copolymers of tetrafluoroethylene with such a small concentration of comonomer that the molecular weight of the resultant polymer is not substantially reduced below that of homopolymer PTFE. The concentration of such comonomer in modified PTFE is less than 1 wt %, preferably less than 0.5 wt %. A minimum amount of at least about 0.05 wt % is generally used to have significant effect.Example comonomer in modified PTFE include perfluoroolefins, notably hexafluoropropylene (HFP) or perfluoro(alkyl vinyl ether) (PAVE), where the alkyl group contains 1 to 5 carbon atoms, with perfluoro(ethyl vinyl ether) (PEVE) and perfluoro(propyl vinyl ether) (PPVE) being preferred, chlorotrifluoroethylene (CTFE), perfluorobutyl ethylene (PFBE), or other similar monomers that introduce relatively sterically bulky side groups into the PTFE polymer chain, as disclosed in U.S.63 / 411 ,777 and WO 2024 / 072861 each incorporated herein by reference in its entirety.

[0121] The tetrafluoroethylene polymer or copolymer is fi brillatable. By fibrillatable is meant that the tetrafluoroethylene polymer is capable of forming nanosized (in at least one dimension (i.e. , <100 nm width) fibrils which can vary in length from submicrometer, to several, to tens of micrometers in length when the tetrafluoroethylene polymer / copolymer is subjected to shear forces.

[0122] The present fluoropolymer composition can include a second polymer different from the first tetrafluoroethylene polymer. The second polymer is one that is capable of forming an aqueous dispersion of fine particles of size substantially similar to that of the tetrafluoroethylene polymer aqueous dispersion, or has solubilityin the aqueous phase of a tetrafluoroethylene polymer aqueous dispersion, and can come into contact with the tetrafluoroethylene polymer primary particles and influence the coagulation of the tetrafluoroethylene polymer primary particles during their coagulation to form agglomerates.

[0123] In one embodiment, the second polymer, includes but is not limited to the group consisting of: fluoropolymers not including the first polymer (tetrafluoroethylene polymer), polyolefins, polyesters, polyamides, polyimides, polyaramides, polyacrylates, polyurethanes, polyethers, polyolethers, polyacrylonitriles, polyphosphazenes, polysiloxanes, polysulfides and polysulfones.

[0124] In one embodiment, the second polymer is selected from the group consisting of: (1) tetrafluoroethylene polymers having a melt creep viscosity within the range of from about 0.5 x 1011poise to about 6.0 x 1011poise and being a tetrafluoroethylene polymer different from the first polymer; (2) tetrafluoroethylene perfluoro(alkyl vinyl ether) copolymers (PFA); (3) fluorinated ethylene propylene copolymers (FEP); (4) fluoroelastomers (FKM); (5) ethylene tetrafluoroethylene copolymers (ETFE); (6) polyvinylidene fluoride polymers (PVDF); (7) polychlorotrifluoroethylene polymers (CTFE); and (8) polyvinyl fluoride (PVF) polymers.

[0125] In one embodiment, the second polymer is a tetrafluoroethylene polymer having a melt creep viscosity within the range of from about 0.5 x 1011poise to about 6.0 x 1011poise and is a tetrafluoroethylene polymer different from that of the first polymer comprising a tetrafluoroethylene polymer.

[0126] In one embodiment, the first polymer comprises a tetrafluoroethylene polymer is a tetrafluoroethylene homopolymer, consisting of repeating units of the tetrafluoroethylene monomer, having a melt creep viscosity of at least about 3.0 x 1011poise, and the second polymer comprises a tetrafluoroethylene polymer is a modified PTFE having concentration of comonomer repeating units less than 1 wt %, and having a melt creep viscosity of at least about 0.5 x 1011poise.

[0127] In preferred embodiments the second polymer is tetrafluoroethylene perfluoro(alkyl vinyl ether) (PFA) copolymer. PFA is a copolymer of tetrafluoroethylene (TFE) and perfluoro(alkyl vinyl ether) (PAVE) monomers in whichthe PAVE monomer linear or branched perfluoroalkyl group contains 1 to 5 carbon atoms. Preferred PAVE monomers are those in which the perfluoroalkyl group contains 1 , 2, 3 or 4 carbon atoms, respectively known 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 made using several PAVE monomers, such as the TFE / perfluoro(methyl vinyl ether) / perfluoro(propyl vinyl ether) copolymer, sometimes referred to as MFA in this field. The PFA may contain about 1-15 wt % PAVE, although a PAVE content of 2 to 8 wt %, preferably 3 to 5 wt %, is the most common PAVE content when a single PAVE monomer is used to form the PFA, the TFE forming the remainder of the copolymer. In one embodiment the MFA includes PMVE, and the composition is about 0.5 to 13 wt % PMVE and about 0.5 to 3 wt % PPVE, the remainder to total 100 wt % being TFE. Preferably, the identity and amount of PAVE present in the PFA is such that the melting temperature of the PFA is greater than about 300°C. The PFA is a fluoroplastic, not a fluoroelastomer. As a fluoroplastic, the PFA is semicrystalline, i.e. , partially crystalline.

[0128] In alternate embodiments the second polymer is perfluorinated ethylenepropylene (FEP) copolymer, a copolymer of tetrafluoroethylene and hexafluoropropylene (HFP). In one embodiment, the HFP content is about 5 to about 17 weight percent in the FEP. In another embodiment, the FEP fluoropolymer comprises TFE / HFP / PAVE terpolymer wherein the HFP content is about 5 to about 17 weight percent and the PAVE content, preferably PEVE, is about 0.2 to about 4 weight percent, the balance being TFE, to total 100 weight percent for the fluoropolymer. In one embodiment, FEP fluoropolymer can be subjected to fluorination for the purpose of reducing the number of thermally unstable end groups (e.g., carboxylic acid end groups). The fluorination can be carried out by known methods with a variety of fluorine radical generating compounds under a variety of conditions as is known in the art, as discussed earlier herein relative to PFA.

[0129] In one embodiment, the second polymer is selected from the group consisting of the fluoroelastomers: (1) vinylidene fluoride / hexafluoropropylene copolymer (VDF / HFP); (2) vinylidene fluoride / hexafluoropropylene / tetrafluoroethylene copolymer (VDF / HFP / TFE); (3) vinylidenefluoride / 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).

[0130] In a preferred embodiment the present FKM fluoroelastomer is a vinylidene fluoride copolymer, more preferably a vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene copolymer.

[0131] In certain embodiments disclosed herein the material for the binder includes:- PFA1 : a copolymer of tetrafluoroethylene and perfluoro(propyl vinyl ether) (PPVE), PPVE content 4 weight percent, having a melt flow rate of 15 g / 10 minutes, and having total carboxylic acid type unstable ends content of about 200 per 106 C atoms. Manufactured by Chemours FC LLC.,- FKM: a copolymer of vinylidene fluoride and hexafluoropropylene (HFP), HFP content 40 weight percent and having a Mooney viscosity of 114 MU, measured at 121 C. Manufactured by Chemours FC LLC.,- PTFE1 : a tetrafluoroethylene homopolymer having a melt creep viscosity of 4.0 x 1011poise manufactured by Chemours FC LLC.,- PTFE3: a modified polymer: a copolymer of tetrafluoroethylene containing 0.128 wt% of copolymerized PPVE (perfluoro(propyl vinyl ether)) as a modifier, having a melt creep viscosity of 1 .47 x 1010poise, manufactured by Chemours FC LLC.

[0132] In certain embodiments disclosed herein the material for the binder includes cocoagulated compositions described herein and disclosed in Provisional Application No. 63 / 411 ,777 (WO 2024 / 072861 ), including but not limited to,PTFE1 +10%PFA1 : cocoagulated composition containing 95 wt% PTFE1 and10 wt% PFA1.,- PTFE2: modified tetrafluoroethylene polymer, containing 0.018 wt% of copolymerized PFBE (perfluorobutyl ethylene) and 0.016 wt% HFP (hexafluoropropylene) modifiers, having a melt creep viscosity of 1 .5 x 1011poise manufactured by Chemours FC LLC.,- PTFE2+5%PFA1 : cocoagulated composition containing 95 wt% PTFE2 and 5 wt% PFA1 ,- PTFE2+10%PFA1 : cocoagulated composition containing 95 wt% PTFE2 and 5 wt% PFA1 ,- PTFE2+ (a vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene copolymer),- PTFE3: modified tetrafluoroethylene polymer, containing 0.128 wt% of copolymerized PPVE (perfluoro(propyl vinyl ether) as modifier, having a melt creep viscosity of 1.47 x 1010poise, manufactured by Chemours FC LLC.,- PTFE3+5%PFA1 : cocoagulated composition containing 95 wt% PTFE3 and 5 wt% PFA1 ,- PTFE3+10%PFA1 : cocoagulated composition containing 95 wt% PTFE3 and 10 wt% PFA1 ,- PTFE3+5%FKM: cocoagulated product containing 95 wt% PTFE3 and 5 wt% FKM (a vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene copolymer), or- PTFE4: modified tetrafluoroethylene polymer, containing 0.038 wt% of copolymerized PFBE (perfluorobutyl ethylene) as modifier, having a melt creep viscosity of 9.16 x 1010poise manufactured by Chemours FC LLC.

[0133] A first electrode embodiment according to the invention disclosed herein comprises, consists essentially of, or consists of, a self-supporting / free standing electrode comprising, consisting essentially of, or consisting of:at least a partially fibrillated binder having exposed surfaces, the binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE containing copolymers, at least one binder-electrolyte derived layer on the exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C between 0.9 volts to 0.3 volts versus Li / Li+, the electrolyte comprises, consists essentially of, or consists of:(a) a non-aqueous electrolyte solvent,(b) a first additive which comprise, consist essentially of, or consist of:(1) an effective amount of at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and an optional second additive, or(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 substituted with a C1-C4 alkyl group, preferably the at least one cyclic additive comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC) and at least one third additive.

[0134] wherein the second additive comprises, consists essentially of, or consists of: (a) an effective amount of at least one unsaturated C=C bond containing compound comprising 1-propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, 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 substituted with a C1-C4 alkyl group, preferably the at least one cyclic additive comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC), and the third additive comprises, consists essentially of, or consists of and effective amount of at least one of: (a) at least one unsaturated C=C bond containing compound comprising 1-propene 1 ,3-sultone,maleic anhydride, 2,5-dihyrofuran, 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 an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine. A second electrode embodiment according to the invention disclosed herein comprises, of consists essentially of, or consists of, at least a partially fibrillated binder having exposed surfaces said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C o a non-aqueous electrolyte solvent, o 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 a C1-C4 alkyl group, preferably the at least one cyclic additive comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC)and o at least additional component selected from: (1 ) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and (2) at least one unsaturated C=C bond containing additive comprising 1 -propene 1 ,3- sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free of vinyl carbonate compounds. said electrode having a reduction peak magnitude between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished by at least 20% relative to that observed using electrodes lacking said at least one binder-electrolyte derived layer.

[0135] A third electrode embodiment according to the invention disclosed herein comprises, of consists essentially of, or consists of,> at least a partially fibri Hated binder having exposed surfaces said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C between 0.9 volts to 0.3 volts versus Li / Li+, said electrolyte comprises: o a non-aqueous electrolyte solvent, an effective amount of one of LiTFSI, LIDFOB, and LiDFOB, and optionally at least one cyclic additive containing fluorine, preferably a compound containing a C2 or C3 fluoroalkene carbonate, most preferably fluoroethylene carbonate (FEC), the electrode having a reduction peak magnitude between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished by at least 40% relative to that observed using electrodes lacking said at least one binder-electrolyte derived layer.

[0136] A further electrode embodiment according to the invention disclosed herein comprises, of consists essentially of, or consists of, at least a partially fibri Hated binder having exposed surfaces said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C between 0.9 volts to 0.3 volts versus Li / Li+, said electrolyte comprises: o a non-aqueous electrolyte solvent, and o an effective amount of maleic anhydride, and optionally at least one cyclic additive containing fluorine, preferably a compound containing anunsubstituted or substituted C2 or C3 fluoroalkene carbonate, most preferably fluoroethylene carbonate (FEC), said electrode having a reduction peak magnitude between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished by at least 40% relative to that observed using electrodes lacking said at least one binder-electrolyte derived layer.

[0137] In any embodiment disclosed herein the polymeric binder comprises one of: a co-coagulated composition containing 95 wt% PTFE1 and 10 wt% PFA1 , a modified tetrafluoroethylene polymer, containing 0.018 wt% of copolymerized PFBE (perfluorobutyl ethylene) and 0.016 wt% HFP (hexafluoropropylene) modifiers, having a melt creep viscosity of 1 .5 x 1011poise, a co-coagulated composition containing 95 wt% PTFE2 and 5 wt% PFA1 , a co-coagulated composition containing 95 wt% PTFE2 and 5 wt% PFA1 , a co-coagulated composition containing >95 wt% PTFE and up to 5 wt%FKM, a modified tetrafluoroethylene polymer, containing 0.128 wt% of copolymerized PPVE (perfluoro(propyl vinyl ether) as modifier, having a melt creep viscosity of 1.47 x 1010poise, a co-coagulated composition containing 95 wt% PTFE3 and 5 wt% PFA1 , a co-coagulated composition containing 95 wt% PTFE3 and 10 wt% PFA1 , a co-coagulated product containing 95 wt% PTFE3 and 5 wt% FKM, or a modified tetrafluoroethylene polymer, containing 0.038 wt% of copolymerized PFBE (perfluorobutyl ethylene) as modifier, having a melt creep viscosity of 9.16 x 1010poise, whereino PFA1 is copolymer of tetrafluoroethylene and perfluoro(propyl vinyl ether) (PPVE), PPVE content 4 weight percent, having a melt flow rate of 15 g / 10 minutes, and having total carboxylic acid type unstable ends content of about 200 per 106C atoms, o FKM is a vinylidene fluoride, hexafluoropropylene and tetrafluoroethylene copolymer with a HFP content 40 weight percent and having a Mooney viscosity of 114 MU, measured at 121 C, o PTFE1 is tetrafluoroethylene homopolymer having a melt creep viscosity of 4.0 x 1011poise, o PTFE2 modified tetrafluoroethylene polymer, containing 0.018 wt% of copolymerized PFBE (perfluorobutyl ethylene) and 0.016 wt% HFP (hexafluoropropylene) modifiers, having a melt creep viscosity of 1 .5 x 1011poise), o PTFE3 is modified tetrafluoroethylene polymer, containing 0.128 wt% of copolymerized PPVE (perfluoro(propyl vinyl ether) as modifier and a melt creep viscosity of 1 .47 x 1010poise, wherein about” is defined to include one of ± 1%, ± 2%, or ± 3% up to the stated value.

[0138] In other embodiments disclosed herein a secondary lithium ion battery, anode or cathode comprises one of the first, second or third electrodes or other described above.

[0139] Other embodiments disclosed herein relate to dry electrodes which comprise, consist essentially of, or consist of graphite, graphene, conductive carbon, and a fibrillated binder, wherein an exposed fibril / node / electrode / binder surface is at least partially covered by a polymer formed from decomposition / polymerization / reaction / electrochemical reduction of a component of a composition comprising lithium electrolyte, additive mixtures which comprise, consist essentially of, or consist of at least one cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imidegroup, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates wherein (a) is preferably at least one of lithium difluoro oxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), lithium trix(oxalato) phosphate (LiTOP), lithium tetrafluoro(oxalato) phosphate (LiTFOP) and, lithium bisoxalatodifluorophosphate (LiBODFP).

[0140] Another embodiment disclosed herein relates to dry electrodes which comprise, consist essentially of, or consist of graphite, graphene, conductive carbon, and a fibrillated fluoropolymer binder, wherein an exposed fibril surface is covered by a polymer formed from decomposition / polymerization / reaction component of a composition comprising lithium electrolyte, at least one unsaturated C2-C4 carbonate solvent, and an additive mixtures which comprise, consist essentially of, or consist of at least one cyclic additive component containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C1-C4 alkyl group, and a second component (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and / or (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates wherein (a) comprises preferably at least one of lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), and lithium bi(fluorosulfonyl) imide (LiFSI), and optionally maleic anhydride.

[0141] Another embodiment disclosed herein relates to dry-processed electrodes which comprise, consist essentially of or consist of graphite, graphene, conductive carbon, and a fibrillated fluoropolymer binder, wherein an exposed binder / node / fibril / electrode surface is at least partially covered by a polymer film formed by a LiPFe solution containing at least two additives selected from lithium difluoro oxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), or lithium bi(fluorosulfonyl) imide (LiFSI), and fluoroethylene carbonate (FEC), preferably wherein the solution comprises an EC / DEC solvent.

[0142] One embodiment disclosed herein relates to a process of forming an electrode by contacting a surface of a graphite electrode containing a fibrillated binder with a LiPFe solution containing at least one of lithium difluoro oxalateborate(LiDFOB), lithium bis(oxalate)borate (LiBOB), and lithium bi(fluorosulfonyl) imide (LiFSI), and fluoroethylene carbonate (FEC), and applying a sweep between or across a voltage range selected from one of 1 .0 V to 0.6 V, 1 .0 V to 0 V, 1.5 V to 0.6V, 1 .5 V to 0 V, 2.0V to 0.6V, or 2.0 V to 0 V.

[0143] One embodiment disclosed herein relates to a process of forming destabilization resistant electrode and an electrode stabilized to electrolyte reduction by contacting a surface of a graphite electrode containing a fibri Hated binder with a film formed by the interaction of the electrolyte in the presence of sweep between or across a voltage range selected from one of 1 .0 V to 0.6 V, 1 .0 V to 0 V, 1.5 V to 0.6V, 1 .5 V to 0 V, 2.0V to 0.6V, or 2.0 V to 0 V, or a sweep between or across a voltage range lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+), wherein the fibrillated binder is a fluoropolymer, such as PTFE and TFE containing copolymers, preferably wherein the binder comprises, consists essentially of, or consists of PTFE, or TFE co-polymers formed with one of hexafluoropropylene (HFP), and / or perfluoro(alkyl vinyl ether) (PAVE) in which the linear 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 the combination of perfluoro(m ethyl vinyl ether)(PMVE) and PPVE, i.e. TFE / PMVE / PPVE copolymer (MFA).

[0144] Certain embodiments disclosed herein relate to a process comprising,> providing an electrode which comprises, consists essentially of, or consists of at least a partially fibrillated binder having exposed surfaces said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, contacting the electrode of with an electrolyte, said electrolyte comprises, consists essentially or consists of, o a non-aqueous electrolyte solvent,o an effective amount of at least one cyclic additive containing fluorine and a carbonyl group, preferably a cyclic fluorocarbon additive, more preferably a C2 or C3 fluoroalkene carbonate, most preferably fluoroethylene carbonate (FEC), and o at least one additional component selected from: at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and at least one unsaturated C=C bond containing compound comprising 1 -propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free of vinyl carbonate compounds applying a sweep between or across a voltage range and forming a reduction inhibiting film or deposit on the exposed surfaces of the electrode, and diminishing the magnitude of the reduction peak using the electrode between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished by at least 20% relative to a film formed in the absence of an effective amount of the at least one cyclic fluorocarbonate additive and the at least one additional component, wherein: the magnitude of the reduction peak between 0.9 V versus 0.3 vs. Li / Li+is diminished by one of 30%, 40%, 50%, 60% or more, relative to an electrode without said film, the sweep between or across a voltage range is selected from one of 1 .0 to 0.6 V, 1 .0 V to 0 V, 1 .5 V to 0.6V, 1 .5 V to 0 V, or 2.0V to 0.6V versus Li / Li+

[0145] Certain embodiments disclosed herein relate to a process diminishing the electrochemical reduction of at least a partially fibrillated binder having exposed surfaces comprising PTFE orTFE containing copolymers and a TFE content of at least 90 wt. %, comprisingcontacting an electrode formed with the polymer and an electrolyte comprising an effective amount of fluoroethylene carbonate (FEC) and additional component selected from: (1) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and (2) at least one unsaturated C=C bond containing compound comprising 1 -propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding vinyl carbonate compounds, wherein (1) the electrode is placed in a secondary lithium ion battery with a counter electrode and at least one sweep is performed where the anode potential is varied from at least 1 .0 V vs. Li / Li+or higher, to at least 0.6 V vs Li / Li+or at least 0.3 V vs Li / Li+, with a lower limit of 0 V vs Li / Li+when a graphite electrode is used, (2) the electrochemical reduction of the polymer and the electrolyte is diminished by at least 20% relative to an electrode with a film produced without the combination of FEC and the additional component, or the electrochemical reduction of the electrode and the electrolyte in a secondary lithium ion battery is diminished by 30%, 40%, 50%, 60% or more.

[0146] In certain embodiment disclosed herein the fluoropolymer binder of the electrode comprises, consists essentially or, or consists of PTFE that has been or can be fibrillated.

[0147] One embodiment disclosed herein relates to an electrode comprising a fibrillated binder, e.g., a binder including a fibrillated PTFE, and a layer formed in the presence of a sweep between or across a voltage range selected from one of 1 .0 V to 0.6 V, 1.0 V to 0 V, 1 .5 V to 0.6V, 1 .5 V to 0 V, 2.0V to 0.6V or 2.0 V to 0 V, or a sweep between or across a voltage range lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 - 0.9 V vs. Li / Li+, and at least fluorinated additive.

[0148] Another embodiment disclosed herein relates to process which comprises, consists essentially of, or consists of applying at least a single sweep between or across a voltage range selected from one of 1.0 V to 0.6 V, 1 .0 V to 0 V, 1.5 V to 0.6V, 1.5 V to 0 V, 2.0V to 0.6V or 2.0 V to 0 V (or a sweep between or across avoltage range lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+to dry-processed carbon electrode comprising a fibrillated binder in contact with a LiPFs solution containing at least two of lithium difluoro oxalate borate (LiDFOB), lithium bis(oxalate)borate (LiBOB), lithium bi(fluorosulfonyl) imide (LiFSI), and fluoroethylene carbonate (FEC).

[0149] Another embodiment disclosed herein relates to a dry-processed carbon electrode comprising a fibrillated binder having a destabilization resistive layer formed in the presence of a dual sweep between or across a voltage range selected from one of 1.0 V to 0.6 V, 1 .0 V to 0 V, 1 .5 V to 0.6V, 1.5 V to 0 V, 2.0V to 0.6V or 2.0 V to 0 V, or a sweep between or across a voltage range lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+, and at least an additive mixture including a fluorinated additive.

[0150] Another embodiment disclosed herein relates to a dry -processed graphite electrode comprising a fibrillated binder having a destabilization resistive layer and an electrode stabilized to electrolyte reduction formed in the presence of a sweep between or across a voltage range selected from one of 1.0 V to 0.6 V, 1 .0 V to 0 V, 1 .5 V to 0.6V, 1.5 V to 0 V, 2.0V to 0.6V or 2.0 V to 0 V, or a sweep between or across a voltage range lower limit potential to a potential more positive than the electrochemical reductive potential of the polymer binder, which for PTFE homopolymer is 0.6 -0.9 V vs. Li / Li+, and at least a fluorinated lithium salt additive, such that at between 0.2 and 0.9 volts of a reverse cycle the magnitude current of the reduction peak is minimized or reduced by at least 40%, 50% or 60%.

[0151] Other embodiments disclosed herein relate to an anode and batteries in which the anode comprises active material that is capable of storing and releasing lithium ions. Suitable anode materials include without limitation lithium titanate, aluminum, platinum, palladium, graphite, graphene, transition metal oxides, and lithiated tin oxide carbon materials such as graphite and mesocarbon microbeads (MCMB ); phosphorus -containing materials such as. conductive black phosphorus; metal oxides such as SnO2, SnO and TiO2; nanocomposites containing antimony or tin, for example nanocomposites containing antimony, oxides of aluminum, titanium,or molybdenum or silicon / carbon / graphite composites and SiOx / carbon / graphite composites.

[0152] In one embodiment disclosed herein the anode active material comprises graphite, graphene, silicon, or SiOx or mixtures thereof.

[0153] In certain embodiment disclosed herein the anode-additive containing electrolyte is assembled in suitable container (not shown) to provide electrochemical cell components and a cathode. Housing materials are well-known in the art and can include, for example, metal and polymeric housings. While the shape of the housing is not particularly important, suitable housings can be fabricated in the shape of a small or large cylinder, a prismatic case, or a pouch. The anode and the cathode may be comprised of any suitable conducting material depending on the type of electrochemical cell.

[0154] A porous separator is present and serves to prevent short circuiting between the anode and the cathode. The porous separator typically includes, but is not limited to a single- ply or multi-ply sheet of a microporous polymer such as polyethylene, polypropylene, polyamide, polyimide or a combination thereof. The pore size of the porous separator is sufficiently large to permit transport of ions to provide ionically conductive contact between the anode and the cathode, but small enough to prevent contact of the anode and cathode either directly or from particle penetration or dendrites which can form on the anode and cathode. Examples of porous separators suitable for use herein are disclosed in U.S. Application SN 12 / 963,927 (filed 09 Dec 2010, U.S. Patent Application Publication No.2012 / 0149852, now U.S. Patent No. 8,518,525), the disclosures of each incorporate herein by reference in their entirety.

[0155] Many different types of materials are known that can function as the cathode. Suitable examples of cathode materials include without limitation graphite, graphene, aluminum, platinum, palladium, electroactive transition metal oxides comprising lithium or sodium, indium tin oxide, and conducting polymers such as polypyrrole and polyvinyl ferrocene.

[0156] Example cathode active particles include metal oxide, metal sulfide, or a lithium metal oxide. In a preferred embodiment, the cathode active particlescomprise a lithium transition metal oxide. Example lithium metal oxides include: lithium nickel manganese cobalt oxide (NMC), lithium manganese oxide (LMO), lithium iron phosphate (LiFePC>4), lithium cobalt oxide (LCO), lithium titanate (LTO), and / or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, cathode active materials can comprise, for example, a layered transition metal oxide (such as LiCoO2 (LCO), Li(NiMnCo)O2 (NMC), LiNi0.8Co0.15AI0.05O2 (NCA)), spinel manganese oxide (such as Li n2O4 (LMO), LiMn1.5Nio.5O4 (LMNO)) or an olivine (such as LiFePO4), LiNiO?, LiNii-xCoxO2, LiNi0.85Co0.1AI0.05O2, LiNi0.33Co0.33Mn0.33O2, LiMn2O4, and combinations thereof.

[0157] 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 ,1 14; 7,718,319; 7,981 ,544; 8,389, 160; 8,394,534; and 8,535,832, and the references therein the disclosure of each incorporated herein by reference in its entirety. By "rare earth element" is meant the lanthanide elements from La to Lu, and Y and Sc.

[0158] In another embodiment the cathode material is an NMC cathode; that is, a LiNiMnCoO cathode, more specifically, cathodes in which the atomic ratio of Ni: Mn: Co is 1 :1 :1 (LiaNia-b-cCObRcO2-dZd) where 0.98 < a < 1 .05, 0 < d < 0.05, b = 0.333, c = 0.333, where R comprises Mn) or where the atomic ratio of Ni: Mn: Co is 5:3:2 (LiaNia-b-cCObRcO2-dZd) where 0.98 < a < 1.05, 0 < d < 0.05, c = 0.3, b = 0.2, where R comprises Mn).

[0159] In another embodiment, the cathode comprises a material of the formula LiaMnbJcC>4Zd, wherein 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.

[0160] In another embodiment, the cathode in the electrochemical cell or lithium ion battery disclosed herein comprises a cathode active material exhibiting greater than 30 mAh / g capacity in the potential range greater than 4.6 V versus a Li / Li"+" reference electrode. One example of such a cathode is a stabilized manganese cathode comprising a lithium-containing manganese composite oxide having a spinel structure as cathode active material. The lithium-containingmanganese composite oxide in a cathode suitable for use herein comprises oxides of the formula LixNiyMzMn2-y-zO4-d, wherein x is 0.03 to 1 .0; x changes in accordance with release and uptake of lithium ions and electrons during charge and discharge; y is 0.3 to 0.6; M comprises 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. Stabilized manganese cathodes may also comprise spinel-layered composites which contain a manganese- containing spinel component and a lithium rich layered structure, as described in U.S. Patent No. 7,303,840, and incorporated herein by reference in its entirety.

[0161] In certain embodiments disclosed herein the diminution of electrochemical reduction is measured by the ratio, of the peak height maximum current in the region of 0.9 V to 0.30 V vs. Li / Li+in the first reductive sweep, to the peak height produced without an effective amount of: (i) at least one cyclic additive containing fluorine and at least one carbonyl group, (ii) at least one a lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, or (iii) at least one unsaturated C=C bond excluding VC and VEC, or combinations thereof in the electrolyte when used in a secondary lithium-ion battery, where the diminution is greater than 80 %.

[0162] In certain embodiments disclosed herein diminution of electrochemical reduction is measured by the ratio of the peak area in the region of 0.9 V to 0.30 V vs. Li / Li+in the first reductive sweep, to the peak height produced without additives, wherein the additives comprise at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group, and optionally at least one of (i) a cyclic additive containing fluorine and at least one carbonyl group, wherein the cyclic additive is unsubstituted or substituted with a C1-C4 alkyl group and (ii) at least one additive containing at least one unsaturated C=C bond free of VC and / or VEC.

[0163] In certain embodiments disclosed herein diminution of electrochemical reduction is measured by the ratio of the peak area in the region of 0.9 V to 0.30 V vs. Li / Li+in the first reductive sweep, to the peak height produced without additives, which additives comprises (i) a cyclic additive containing fluorine and at least onecarbonyl group, wherein the cyclic additive is unsubstituted or substituted with a Ci- 04 alkyl group and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding VC and VEC, preferably when used in a secondary lithium-ion battery, where the diminution is greater than 80 %.

[0164] One embodiment of the invention disclosed herein relates to a binder which comprises film coated fibrillated PTFE / TFE containing polymers and copolymers,.

[0165] In certain embodiments disclosed herein the anode comprises, consists essentially of, or consists of graphite active anode powder, Super P conductive carbon, a PTFE or TFE containing binder and film derived from fluoride components with prevents / reduces reduction of the binder, and prolongs the life of the anode by a sweep between or across a voltage range applied to a LiPFe solution containing at least two lithium salts selected from lithium difluoro oxalate borate(LiDFOB), lithium bis(oxalate)borate (LiBOB), LiTOP (lithium trix(oxalato) phosphate) and LTFOP (lithium tetrafluoro(oxalato) phosphate), lithium bisoxalatodifluorophosphate (LIBODFP), lithium bi(fluorosulfonyl) imide (LiFSI), and LiTFSI.

[0166] SEM images of a PTFE binder on the electrode before and after cycling in the presence of EC / EMC or EC / DEC+5% FEC electrolyte are shown in Figs. 2 (a)- (c). As shown, the quantity of fibrils in a fresh electrode Fig. 2 decreases the most after 1 cycle in the presence of EC / EMC, destabilization of fibrils occurred, which decreased with the addition of a lithium salt lithium fluoro carbonate or borate additive, resulting in the retention of a significant number of fibrils to ensure a good binding force.EXAMPLES

[0167] The disclosed methods provide an electrode TFE fluoropolymer for use as binder in a lithium-ion secondary battery anode, the fluoropolymer has the physical property to provide inter-particle fibrillation without initiation of fibrillation, until the fluoropolymer is homogenous. This provides fibrillation characteristics whichcomplement the chemical and physical properties necessary for the anode, most specifically, reduced destabilization, improved columbic efficiency and better cycling life.

[0168] Fluoropolymer binder TE-1 used in the examples 1 A, 1 B, 2A, 2B, comparative AA, comparative AB, 3A, 3B, comparative DA, and 6A, 7A, 7B, 8A, 8B, 9A, 9B, 10, 1 1 , E, FA, FB and G is commercially available from Chemours FC LLC or can be prepared from aqueous dispersions of tetrafluoroethylene polymer using known methods. Dispersion processes for polymerizing fluorinated monomers in aqueous media are known and prepared using established commercial technology, for example, as taught in U.S. Patent No. 4,576,869 granted to Malhotra, the disclosure of which is incorporated herein by reference in its entirety.Preparation of PTFE Binder TE-1

[0169] To a nominally 10-gallon jacketed, cylindrically-shaped stainless steel reactor with an aspect ratio of 1.5 equipped with a paddle stirrer was charged 600 grams of natural paraffin wax and 4.3 g of succinic acid and the reactor was sealed. After adding 24.1 liters of demineralized water, the reactor was heated to 65 °C, the reactor was agitated at 70 RPM then pressured to 400 PSIG with nitrogen and checked for leaks. After venting, an aqueous solution containing 0.7 g perfluoropolyether acid polymerized from hexafluoropropylene oxide with a number average molecular weight of approximately 1500 Daltons, 147 g of HFPO dimer acid, ammonium salt, and 61.8 g demineralized water was added. The agitator was stopped and the reactor was purged with TFE to greater than 25 PSIG and evacuated to at least -2.0 PSIG three times. The agitator was restarted and the reactor was charged with TFE until a pressure of 400 PSIG was reached. To start the polymerization, 180 mL of a 0.015% (m / v) aqueous solution of potassium permanganate (KMnC ) were added at a rate of 80 mL / min, then KMnO4 injection continued at 3.5 mL / min until 4.7 kg of TFE had been charged from the start of KMnC>4 injection. Also at 4.7 kg of TFE charged, the temperature was increased to 85 °C. After a total of 10.9 kg of TFE were added since kickoff, the TFE addition valve was closed, the agitator was stopped and the reactor was vented slowly over 10 minutes. When the reactor pressure reached 1-2 PSIG, nitrogen was added to give a slow pressure rise to 5 PSIG. The reactor was evacuated for 1 minute thenthe 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 a raw dispersion particle size of 218.5 nm. After draining the dispersion, 495 g of coagulum, containing water, paraffin wax and polymer, were left behind in the reactor.

[0170] The polymer was coagulated in a 3L vessel by diluting the above dispersion to about 14 wt% solids and by adding about 3.7% by mass (dry weight) of a 20 wt% aqueous ammonium carbonate solution followed by vigorous agitation until the polymer fully separated from the water. The polymer was dried in a static oven at 150 °C for 24 hours and gave an SSG of 2.1672Preparation Binder TE-2 with FKM dispersion used in Comparative Examples FC, and examples, 4A, 5A.

[0171] Preparation of FKM dispersion: FKM dispersion was prepared by continuous emulsion polymerization, carried out at 108°C in a well-stirred 2.0-liter stainless steel liquid full reaction vessel. An aqueous solution, consisting of 6.09 g / hour (g / h) ammonium persulfate, 0.70 g / h sodium sulfite, and 0.91 g / h sodium hydroxide in deionized water, was fed to the reactor at a rate of 10 L / hour. The reactor was maintained at a liquid-full level at a pressure of 6.2 MPa by means of a backpressure control valve in the effluent line. After 30 minutes, polymerization was initiated by introduction of a gaseous monomer mixture consisting of 1547 g / h vinylidene fluoride ( F2), and 11231 g / h hexafluoropropylene (HFP) fed through a diaphragm compressor. After 2.0 hours, effluent dispersion was collected for 5 hours. The effluent polymer dispersion contained 20 wt.% solids, was separated from residual monomers in a degassing vessel at atmospheric pressure

[0172] A modified tetrafluoroethylene polymer, containing 0.128 wt% of copolymerized PPVE (perfluoro(propyl vinyl ether)) as modifier, having a melt creep viscosity of 1 .47 x 1010poise, manufactured by Chemours FC LLC.

[0173] Preparation of Binder TE-2: To a 3-liter glass vessel equipped with four stainless steel baffles was added 110 mL of demineralized water, 1643 mL of the dispersion of modified tetrafluoroethylene polymer with a polymer solids of 18.5%,104 mL of FKM aqueous dispersion with a polymer solids of 15.69%, and 43 mL of a 20% ammonium carbonate solution. A mechanical stirrer equipped with two 4-blade turbine agitators attached to a central shaft, was added to complete the apparatus. Dimensions of the full coagulator assembly are as follows. The 3 L glass container has an inner diameter of 13 cm. The baffles are attached with a thin metal ring and have a height of 13 cm and a width of 1 .5 cm. The two agitators are separated by 6 cm on the shaft and comprised of four blades (blades are 1 .5 cm wide and 4.5 cm long) with a 45-degree pitch. The rotation is in the direction to create an upward flow of fluid. With the lid in place (through which the agitator shaft runs), the contents of the coagulator were stirred at 800 rpm with a Caframo BDC3030 motor until the solid co-coagulated polymer was sufficiently separated from the water. After decanting, the wet powder was washed with 1000 mL of demineralized water then filtered through cheesecloth. The powder was dried at a temperature of 150 C in a tray oven to yield the co-coagulated fluoropolymer composition.Electrolyte Formulation Examples

[0174] Examples 1A, 1 B: 1.2 M LiPF6+ EC / DEC (3:7 by volume) + 1 wt % LiBOB + 4 wt % FEC:0.1579 grams of lithium bis(oxalate)borate (LiBOB, Gotion, battery materials) and 0.6316 g of fluoroethylene carbonate (FEC, Gotion, battery materials) were combined with 15 grams of a standard electrolyte 1. 2M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0175] Examples 2A, 2B: 1 .2 M LiPFe + EC / DEC (3:7 by volume) + 10 wt % LiTFSI1.6667 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), Gotion, battery materials) was combined with 15 grams of a standard electrolyte 1.2M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox

[0176] Comparative Examples AA, AB: 1 .2 M LiPFe + EC / DEC (3:7 by volume)A standard electrolyte containing 1.2 M LiPFe, ethylene carbonate (EC) and diethylcarbonate (DEC) was obtained from Gotion, Freemont CA.

[0177] Comparative Example FC: 1 .2 M LiPFe + EC / DEC (3:7 by volume) + 5 wt % FEC0.7985 g of fluoroethylene carbonate (FEC, Gotion, battery materials) were combined with 15 grams of a standard electrolyte 1 ,2M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0178] Comparative Example CA:1 .2 M LiPFe + EC / DEC (3:7 by volume)A standard electrolyte was used containing 1 .2 M LiPFe, ethylene carbonate (EC) and diethylcarbonate (DEC) was obtained from Gotion, Freemont CA.

[0179] Example 4A:1 .2 M LiPFe + EC / DEC (3:7 by volume) + 5 wt % LiFSI0.7895 g of lithium bi(fluorosulfonyl) imide (LiFSI), Gotion, battery materials) was combined with 15 grams of a standard electrolyte 1 ,2M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0180] Example 5A:1 .2 M LiPFe + EC / DEC (3:7 by volume) + 5 wt % maleic anhydride0.7895 g of maleic anhydride (Sigma Aldrich, Milwaukee, Wl 99.8 %) was combined with 15 grams of a standard electrolyte 1.2M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0181] Comparative Example DA:1.2 M LiPFe + EC / DEC (3:7 by volume)A standard electrolyte was used containing 1 .2 M LiPFe, ethylene carbonate (EC) and diethylcarbonate (DEC) was obtained from Gotion, Freemont CA.

[0182] Example 6A:1 .2 M LiPFe + EC / DEC (3:7 by volume) + 5 wt % LiTFSI0.7895 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, Gotion, battery materials) was combined with 15 grams of a standard electrolyte 1.2 M LiPFeEC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0183] Example 7A, 7B:1.2 M LiPFe + EC / DEC (3:7 by volume) + 1 wt % LiDFOB0.7895 g of lithium difluoro oxalate borate (LiDFOB Gotion, battery materials) was combined with 15 grams of a standard electrolyte 1.2 M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0184] Examples 8A, 8B: 1 .2 M LiPF6 + EC / DEC (3:7 by volume) + 1 wt % Li BOB0.7895 g of lithium bis(oxalate)borate (LiBOB, Gotion, battery materials) was combined with 15 grams of a standard electrolyte 1.2 M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0185] Example 9A, 9B:1.2 M LiPFe + EC / DEC (3:7 by volume) + 1 wt % LiDFOB + 4 wt % FEC0.1579 grams of lithium difluoro oxalate borate (LiDFOB Gotion, battery materials) and 0.6316 g of fluoroethylene carbonate (FEC, Gotion, battery materials) were combined with 15 grams of a standard electrolyte 1.2M LiPFe -EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0186] Comparative E: 1 .2 M LiPFe + EC / DEC (3:7 by volume)A standard electrolyte was used containing 1 .2 M LiPFe, ethylene carbonate (EC) and diethylcarbonate (DEC) was obtained from Gotion, Freemont CA.

[0187] Comparative FA, FB: 1 .2 M Li PF6+ EC / DEC (3:7 by volume) + 5 wt % 1 ,3 propane sultone0.8001 g of 1 ,3 propane sultone (Gotion battery materials) was combined with 14.9987 grams of a standard electrolyte 1 .2 M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.

[0188] Comparative G: 1 .2 M LiPFe + EC / DEC (3:7 by volume) + 5 wt % succinic anhydride0.7725 g of succinic anhydride (Sigma-Aldrich, St. Louis, MO, 99 + % purity ) was combined with 15.0390 grams of a standard electrolyte 1 .2 M LiPFe EC / DEC obtained from Gotion (Fremont, CA) to prepare the electrolyte mixture in an inert atmosphere drybox.Table 1 : Example Weight Fraction:Table 1 : Example Weight Fraction (continued):Table 1 : Example Weight Fraction (continued):Fabrication and testing procedures for all examplesAnode Electrode Fabrication

[0189] T est anodes were prepared using the present fluoropolymer compositions by the following procedures:

[0190] Approximately 10 g of a powder mixed was created using 90 % graphite (Amsted Graphite Materials, Anmoore, VA), % Super P carbon black, and 5 wt % of the polymer binder. The graphite and super P carbon black were combined in a mortar and pestle and mixed for approximately 15 minutes.

[0191] This mixture was combined with the fluoropolymer binder into a 250 ml plastic bottle with approximately ten ZrO2(10 mm in diameter) milling media and rolled for about 30 minutes. The powder was separated from the milling media.

[0192] A free standing film was created by placing 3 grams of the mixture onto a small glass mortar and pestle. This material was manually ground until the powder formed a solid flake. The flakes were placed onto a hot plate with a piece of Kapton® film and heated to 100 C. Using a manual steel roller, the flakes were rolled at 100 C until a uniform film was formed.

[0193] A TMAX calender was used. The calendering rolls were heated to 50 C for at least 1 hour before use. The thickness of the free-standing film was measured prior to calendering. The calendering gap was set at 50-100 pm below the starting film thickness. For example, if the starting free standing film was 480 pm, the gap distance was initially set to 400 pm. The free standing film was placed on the roller. The film was passed through the calendering gap two times. At larger gap distances, the film will fall off the rollers. A piece of paper was held below the rolls to catch the film. The calendering gap was reduced by 50 micron steps. For each step, the film was passed through the calendering rollers two times. Eventually, the film will stick to the roller, and the film was run through the calendering device in this manner. The calendered gap was continually lowered in 50 micron increments until a final thickness of about 100 microns was reached.Cell fabrication:

[0194] The electrode disks (12 mm in diameter) were punched from the free standing (self-supporting) film and dried at 120 °C under vacuum at least 8 hours. 2032 type coin cells were assembled with a lithium metal counter electrode, Celgard 2325 separator and the electrolyte compositions described herein.

[0195] An anode was prepared by blending 90% graphite active anode powder, 5% Super P conductive carbon, and 5% PTFE binder, as described above using PTFE binder TE-1 . Figure 1 shows the discharge and charge potential profiles of the 1stcycle of the graphite half cells with TE-1 as binder, in EC (CtW CyEMC (CH3CH2OC(O)OCH3)[Comparative Example AA] and EC / DEC+5% FEC(fluoroethylene carbonate, 4-fluoro-1 ,3-dioxolan-2-one) electrolytes [Example 3A], The efficiency of the cell in EC / DEC+5% FEC is 76.3%, but it is only 46.3% in EC / EMC electrolyte. As a result of including FEC in the electrolyte, the efficiency increased by almost 65%.Cyclic Voltammetry Measurement:

[0196] The cyclic voltammetry examples in different electrolyte compositions was measured in a Bio-Logic potentiostat using the lithium metal half cells assembled as described above The cyclic voltammetry testing is preferably comprises scanning from 0 to 1 .5 V potential vs Li / Li+at 0.05 mV / sec scan rate. The peak height was measured in the potential region of 0.9 to 0.3 V vs. Li / Li+during the first reductive sweep in the cyclic voltammetry measurement. In all cases, an estimated baseline correction was applied to the peak height determination. In the tables below, this peak height was divided by the peak height (or the average peak are) of the comparative example in the table. A lower ratio means that the reductive current observed is lower in the 0.9 to 0.3 V region in the cyclic voltammetry measurement.

[0197] Alternatively, the peak area was measured in the potential region of 0.9 V to 0.30 V vs. Li / Li+ during the first reductive sweep in the cyclic voltammetry measurements. In this case, integration relies on a normalization of the CV data set to a fixed line at the current value present at 0.9V, i. e. , the value of current at 0.9V is subtracted from the entirety of the data set prior to integration. The area under the curve after this normalization was calculated via 5 techniques: Reimann sums with midpoint, right, and left divisions and trapezoidal sum with uniform and non-uniform divisions were determined. The value of these five techniques were then averaged for a final integral value. A reference describing the various integration methods is copied below, from Libretexts Mathematics, section 2.5, Numerial Integration- Midpoint, Trapezoid and Simpson’s rule and incorporated herein by reference, https: / / math.libretexts.org / Courses / Mount_Royal_University / MATH_2200%3A_Calcu lus_for_Scientists_ll / 2%3A_Techniques_of_lntegration / 2.5%3A_Numerical_lntegrati on Midpoint%2C_Trapezoid%2C_Simpson%27s_rule#:~:text=The%20most%20co mmonly%20used%20techniques,definite%20integral%20using%20trapezoidal%20a pproximations.

[0198] In the tables below, this peak area was divided by the peak area (or the average peak area) of the comparative example in the table. A lower ratio means that the reductive current observed is lower in the 0.9 to 0.3 V region in the cyclic voltammetry measurement.

[0199] The Cyclic Voltammetry data for examples corresponding to the scans of Figures 3-7, are used to determine Peak Height Ratios (reductive peak between 0.9 and 0.3 V vs. Li / Li+, and are tabulated in Table 2, below. The numerically integrated peak ratios in the 0.9 to 0.3 V region are also shown.

[0200] The data of Table 2 reveals that using a lithium salt compound in the electrolyte reduces the electrode reduction by at least about 40%. In some cases, the reduction is improved by more than 80 %. This improvement will increase the amount of cyclable lithium in the battery and will also improve the mechanical integrity of the electrode.

[0201] As shown best shown in the figures, Fig. 3 compares the cyclic voltammetry of Examples 1 A, 1 B, 2A, and 2B with that of Comparative example DA; Fig. 4 compares the cyclic voltammetry of Examples 6A, 7A and 7B with that of Comparative example DA.

[0202] Fig. 5 compares the cyclic voltammetry of Examples 8A, 8B, 9A and 9B with that of Comparative example DA; and

[0203] Fig. 6 compares the cyclic voltammetry of Examples 9A with that of Comparative example DA.

[0204] The data of Table 3, derived from and depicted in Fig. 7, reveals that using a lithium salt compound in the electrolyte and an electrode made with binder TE-2, reduces the electrode reduction by at least about 40% compared with Comparative Example 3A. In all cases, an estimated baseline correction was applied to the peak height determination.

[0205] Comparative CA, derived from an electrode containing the TE-2 binder, shows an estimated numerical integration value of the reduction peak between 0.9 and 0.3 V versus Li / Li+ in the cyclic voltammetry measurement which is very similar to that observed in comparative example DA, which is derived using the anode containing the TE-1 binder. For comparative example CA, this reductive peak integrated magnitude is 0.027 versus 0.024 for comparative example DA. In both cases, the electrolyte was 1.2 M LiPFe + EC / DEC (3:7 by volume), which means that the data from the two sets using binder TE-1 and TE-2 can be compared.

[0206] An electrolyte containing 5 wt % FEC is shown in comparative example FC. Here, the numerically integrated reduction peak ratio to comparative CA (measured between 0.9 to 0.3 V vs Li / Li) is 0.298. This is a ratio of the integrated reduction peak area normalized to the peak area of comparative example CA. This value is significantly higher than the value observed in examples 1 A, 1 B of 0.20 and 0.23 derived from the numerically integrated area normalized to the reductive peak area of comparative DA. In this case, an electrolyte containing 1 wt % LiBOB and 4 wt % FEC was used, and this shows the synergy between LiBOB and FEC in terms of reducing the reduction peak magnitude between 0.9 and 0.3 versus Li / Li+ in the cyclic voltammetry experiment, versus FEC alone. Similarly, example 9B shows the synergy between LiDFOB and FEC with a reductive peak magnitude ratio (normalized to integrated peak area of comparative DA) of 0.26 using a formulation containing 1 wt % LiDFOB and 4 wt % FEC.

[0207] Comparative Examples: Additive-1 ,3 propane sultone / succinic anhydride

[0208] The Cyclic Voltammetry data for Comparative examples E, FA, FB and G , used to determine Peak Height Ratios (reductive peak between 0.9 and 0.3 V vs.Li / Li+, and are tabulated in Table 4 below. The data of Table 4 shows that the use of 1 ,3 propane sultone had a detrimental effect on electrode stabilization, whereas succinic anhydride has a minor beneficial effect.

[0209] As shown in Figures 3-7 scans, reduction peaks using a graphite electrode formed with a PTFE binder were diminished to a value of 0.17 for examples 1A, 1 B, 2A, 9A and 9B compared with example DA (Comparative). The remaining examples similarly had diminished reduction peaks. As currently understood, the fluorinated electrolytes additive FEC may decompose / polymerize / react during the first cycle to form a product formed from IJ2CO3 and LiF on the electrode and the PTFE fibrils and graphite. One possible mechanism for the FEC polymerization is shown below.

[0210] This layer effectively resists destabilization of the polymer to prevent the further reduction which have been semi-quantified by estimating the peak height in the potential region of 0.90 V versus 0.3 V vs. Li / Li+during the first reductive sweep in the cyclic voltammetry measurement.

[0211] There are several mechanisms wherein the film layer(s) is derived from an electrolyte comprising one or more of: (i) at least one lithium salt additive comprising fluorine and one or more of an oxalate, borate, sulfonyl or sulfonyl imide group, (ii) at least one additive (ii) containing at least one unsaturated C=C bond excluding VC and / or VEC, (iii) at least one cyclic additive containing fluorine, or a combination of two or more of (i), (ii) and (iii). These mechanisms include decomposition, incorporation, polymerization (as described herein), co-polymerization with other electrolyte components, and co-polymerization of a partially reduced product from the polymer, or combinations of the above.CHARACTERIZATION PTFE DEGRADATION BY X-RAY SCATTERING

[0212] Examples 10 and 11

[0213] The x-ray scattering samples were collected by decrimping the coin cell and removing the anode after 3 cycles of cyclic voltammetry testing within an Argon glove box. Example 10 was derived from comparative example CA and Example 11 uses the electrode of example 3A and Example 12 is derived from the pristine anode used for Examples 10 and 11.

[0214] The samples where sealed in a Kapton tape to remove the possibility of air exposure. These samples where then mounted in the x-ray scatteringinstrument and the measurement was taken under vacuum. The wide-angle x-ray scattering data was collected using a Xenocs (Denmark) Xuess 2.0 combined smallangle scattering / wide-angle scattering instrument. This instrument uses a copper high-flux source and a multi-panel two-dimensional (2D) detector. The use of a 2D detector for the current work is extremely important for capturing the <5% weight PTFE within the electrode, it is unclear if this same fidelity of data could be capture with a one-dimensional (1 D) detector. The samples were scanned for 3 minutes with a beam cross-section of 2mm x 2nmm to generate the 2D at a sample-to-detector distance 72mm. Scans under identical conditions were also taken for the Kapton tape that was used to seal the sample. The intensity of the pure Kapton diffraction signal was then scaled to match the magnitude of the Kapton signal within the electrode samples and this signal was subtracted from the 2D diffraction pattern via matrix arithmetic. The 2D diffraction signal was then integrated resulting in the 1 D diffraction data shown within the current patent. All data processing was done using the program XSACT.

[0215] At this point, the area under the curve, off of a liner approximation was taken for the primary peaks corresponding to the PTFE binder, and this value was related back to the peak height for the pristine anode (Example 12). The ratio, given as a percent, of peak area after cycling over pristine peak area is presented in Table 5 as PTFE retention. It can be seen from this data that the scattering intensity of the PTFE in system with FEC additive (Example 11) is double the intensity of the peak in the sample with no additives, indicating significant protection of the PTFE binder when additives are used, and the retention of more PTFE structure.

[0216] Figure 8 relates to the scattering intensity for pristine and cycled electrodes and the graphite and PTFE electrode components. Figure 9 illustrates the scattering intensity for , VC, MA and FEC additives.OTHER EMBODIMENTSOE-1. An electrode includes a polymer upon which a film layer or deposit can form, the polymer comprises at least a binder for the electrode, and the electrode comprises, consists essentially of, or consist of: a material selected from graphite, graphene, mesocarbon microbeads (MCMB), silicon, or SiOxor mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composite, lithiated tin oxide, conductive black phosphorus, SnO?, SnO, nanocomposites containing antimony, oxides of aluminum titanium and molybdenum, and a polymer selected from one of: (1 ) non-TFE containing polymers, (2) fibrillated TFE containing polymers, (3) fibrillated TFE containing copolymers, (4) fibrillated TFE containing co-coagulated polymers, (5) non-fibrillated TFE containing polymers, (7), non-fibrillated TFE containing copolymers, (8) non- fibrillated TFE containing co-coagulated polymers, or (10) mixtures of one of (i) fibrillated. TFE containing polymers, copolymers, and co-coagulated polymers and (ii) non-fibrillated. TFE containing polymers, non-fibrillated TFE containing copolymers, and non-fibrillated TFE co-coagulated polymers.OE-2. An electrode comprises, consists essentially of, or consist of: a material selected from graphite, mesocarbon microbeads (MCMB ), silicon, or SiOx or mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composite, lithiated tin oxide, conductive black phosphorus; SnC>2, SnO, nanocomposites containing antimony, oxides of aluminum titanium and molybdenum, and a polymer selected from one of: (1 ) non-TFE containing polymers, (2) fibrillated TFE containing polymers, (3) fibrillated TFE containing copolymers, (4) fibrillated TFE containing co-coagulated polymers, a film layer or deposit is an electrochemically derived film or deposit formed from the electrode polymer, an electrolyte, and additives selected from (A) at least one lithium salt additive comprising one or more of an oxalate, borate,chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, optionally containing at least one cyclic additive containing fluorine and a carbonyl group or, (B) mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).OE-3. The electrolyte of OE-1 or OE-2 wherein the additive comprises LiBOB +FEC.OE-4. The electrolyte of OE-1 or OE-2 wherein the additive comprises LiFSI.OE-5. The electrolyte of OE-1 or OE-2 wherein the additive comprises LiFSI+FEC.OE-6. The electrolyte of OE-1 or OE-2 wherein the additive comprises LiDFOB.OE-7. The electrolyte of OE-1 or OE-2 wherein the additive comprises LiBOB.OE-8. The electrode of OE-4 wherein the additive comprises LiDFOB + FEC.OE-9. The electrode of OE-4 wherein the additive comprises LiBOB + FEC.OE-10. The electrode of OE-4 wherein the additive comprises LiFSI.OE-11. The electrode of OE-4 wherein the additive comprises LiFSI+ FEC.OE-12. The electrode of OE-4 wherein the additive comprises LiDFOB.OE-13. The electrode of OE-4 wherein the additive comprises LiBOB.OE-14. The electrode of OE-4 wherein the additive comprises LiDFOB + FEC.OE-15. The additive of any of OE-1 -OE14 wherein each of the additives is independently present in an amount of >0.5 wt.% up to the solubility limit of the additive in the electrolyte, e.g., in an amount of 1 wt. %, 2 wt.%, 3 wt. %, 4 wt.%, 5 wt. %, 7 wt. %, 8 wt.%, 9 wt. %, 10 wt.% or higher and all increments and ranges therebetween.OE-16. Any OE embodiment above wherein the electrolyte comprises LiPFe + EC / DEC (3:7 by volume).OE-17. Any OE embodiment above wherein the at least one unsaturated C=C bond optionally excludes at least one of VEC and VC.OE-18. Any OE embodiment above wherein an electrolyte is present, and the electrolyte comprises one of a 0.8M, 1.0 M, 1.2M,or 1.4M LiPFe-EC / DEC solution.OE-19. Any OE embodiment above wherein an electrolyte is present, and the electrolyte comprises one of a 0.8M, 1.0 M, 1.2M, or 1.4M of one or more of lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethyl) tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium perchlororate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate salts.OE-20. An electrolyte which comprises one of a 0.8 M, 1 .0 M, 1 .2 M, or 1.4 M solution comprising one or more of lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethyl) tetrafluorophosphate (LiPF^CFs ), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium perchlororate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate electrolyte salt, a solvent, and (i) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, and at least one cyclic additive containing fluorine, or mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates. More preferably, the at least one cyclic additive containing fluorine andat least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is un substituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC).OE-21. An electrolyte which comprises one of a 0.8 M, 1.0 M, 1 .2 M, or 1.4 M solutions of one or more of lithium hexafluorophosphate (Li PFe) , lithium bis (trifluoromethyl) tetrafluorophosphate (LiPF4(CFs)2), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium perchlororate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate electrolyte salt, a solvent, and stabilizing additives selected from: (A) (i) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, (ii) at least one additive (ii) containing at least one unsaturated C=C bond, (iii) at least one cyclic additive containing fluorine, or a combination of two or more of (i), (ii) and (iii), e.g., (i) and (ii), (ii) and (iii). (i) and (iii), or (i), (ii) and (iii) with the proviso that the one additive (ii) containing at least one unsaturated C=C bond optionally excludes vinyl ethylene carbonate (VEC), vinylene carbonate (VC), or (B) comprises mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC)OE-22. A process making any electrode embodiment above comprising placing the electrode in contact an electrolyte selected from one a 0.8M, 1 .0 M, 1 .2 M, or 1 .4 M one or more of lithium hexafluorophosphate (Li PFe), lithium bis (trifluoromethyl) tetrafluorophosphate (LiPF4(CF3)2), (A) lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium perchlororate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonate solution, additives selected from (i) at least one lithium salt additive comprising one or more of an oxalate,borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, (ii) at least one additive containing at least one unsaturated C=C bond, (iii) at least one cyclic additive containing fluorine, or a combination of two or more of (i), (ii) and (iii), e.g., (i) and (ii), (ii) and (iii). (i) and (iii), or (i), (ii) and (iii); or, (B) mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding ethylene carbonates. More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC), and applying a sweep between or across a voltage range sweep between or across a voltage range is selected from one of 1.0 V to 0.6 V, 1 .0 V to 0 V, 1.5 V to 0.6V, 1.5 V to 0 V, or 2.0V to 0.6V thereby forming one or more reduction diminishing films or deposits on the polymer of the electrode with the proviso that the one additive containing at least one unsaturated C=C bond optionally excludes vinyl ethylene carbonate (VEC), vinylene carbonate (VC).OE-23. The process of any forming a film derives from the interaction of at least one of decomposition, absorption, assimilation, infusion, incorporation, polymerization, co-polymerization with other electrolyte additives and polymeric electrode components, co-polymerization with a partially reduced polymer of a polymeric component of the electrode, or combinations of one of the polymeric components or materials of the electrode and the electrolyte compositions which include, in addition to the electrolyte, additives comprising LiDFOB, LiBOB, LiFSI, LiTFSI, LiDFOB + FEC, LiBOB + FEC, LiFSI + FEC, or LiTFSI + FEC.OE-24. A battery comprising: (a) one of a 0.8M, 1 .0 M, 1 .2 M, or 1 ,4M electrolyte composition comprising one or more of lithium hexafluorophosphate (LiPFe), lithium bis (trifluoromethyl) tetrafluorophosphate (LiPF4(CF3)2), lithium bis(fluorosulfonyl)imide LiFSI, lithium bis (trifluoromethanesulfonyl) imide LiTFSI, lithium perchlororate, lithium hexafluoroarsenate, or lithium trifluoromethanesulfonateelectrolyte salt containing solvents, (b) one of (A) or (B), wherein (A) comprises at least one lithium salt additive (i) comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine,(ii) at least one additive (ii) containing at least one unsaturated C=C bond, (iii) at least one cyclic additive containing fluorine, or a combination of two or more of (i), (ii) and (iii), e.g., (i) and (ii), (ii) and (iii). (i) and (iii), or (i), (ii) and (iii), and (B) comprises mixtures of additives, which comprise, consist essentially of, or consist 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 C1-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine, and (b) at least one additive containing at least one unsaturated C=C bond excluding vinyl ethylene carbonate (VEC), vinylene carbonate (VC). More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (EEC), and an (c) an anode electrode with an electrochemically derived film formed from the possible interaction of (a), (b) a polymer component of (c) in the presence of a sweep between or across a voltage range sweep between or across a voltage range is selected from one of 1 .0 V to 0.6 V, 1 .0 V to 0 V, 1 .5 V to 0.6V, 1 .5 V to 0 V, or 2.0V to 0.6V.OE-25. The battery of OE-24 wherein the electrolyte comprises one of a 0.8M, 1 .0 M, 1.2M,or 1.4M LiPFe-EC / DEC solution and the additive comprises LiDFOB, LiBOB, LiDFOB + FEC, LiFSI, LiFSI+ FEC, LiBOB + FEC, LiFSI, or LiDFOB.OE-26. In combination at least one layer and a TFE material of an electrode in a lithium ion battery wherein the film layer(s) is derived from an ion conducting electrolyte comprising at least one lithium salt additive comprising one or more of an oxalate, borate, sulfonyl or sulfonyl imide groups, and optionally fluorine group, and optionally (ii) at least one additive having at least one unsaturated C=C bond, and(iii) at least one cyclic additive containing fluorine; or (iv) a combination of two or more of (i), (ii) and (iii) mixtures of additives, which comprise, consist essentially of, or consist 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 Ci-C4 alkyl group, and one of (a) at least one lithium salt additive comprising one or more of an oxalate, borate, chlorate, sulfonyl or sulfonyl imide group, or phosphate group and optionally fluorine and (b) at least one additive containing at least one unsaturated C=C bond excluding vinyl ethylene carbonate (VEC), vinylene carbonate (VC). More preferably, the at least one cyclic additive containing fluorine and at least one carbonyl group comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (EEC).OE-27. An electrode is a component of a secondary lithium ion battery and exhibits an electrochemical reduction between 0.9 V versus 0.3 V vs. Li / Li+that is diminished by at 30% relative to and an electrode without the film layer derived from one of LiDFOB., LiBOB, LiDFOB + FEC, LiFSI, LiFSI+ FEC, LiBOB + FEC, LiFSI, LiDFOB, maleic anhydride in the electrolyte, and the electrochemical reduction in a secondary lithium ion battery is diminished one 40%, 50%, 60% or more.OE-28. An electrode where the diminution of electrochemical reduction is measured by a ratio of the peak height maximum current in the region of 0.9 V to 0.3 V vs. Li / Li+in a first reductive sweep, to peak height produced LiDFOB., LiBOB, LiDFOB + FEC, LiFSI, LiFSI+ FEC, LiBOB + FEC, LiFSI, LiDFOB, maleic anhydride in the electrolyte when used in a secondary lithium-ion battery.OE-29. The electrode in any of OE embodiment disclosed herein, wherein the additive contains at least one unsaturated C=C bond is selected from maleic anhydride, 2,5-dihyrofuran allyl ethyl carbonate, allyl methyl carbonate, allyl phenyl carbonate and excludes VC or VEC.OE-30. An electrode wherein the cyclic carbonate containing fluorine is selected from fluoroethylene carbonate (FEC), 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), preferably fluoroethylene carbonate (FEC).OE-31. Any OE above including wherein the binder polymer is selected from one of: a polymer selected from one of: (1) at least partially fibrillated TFE containing polymers, (2) at least partially fibrillated TFE containing copolymers, (3) at leastpartially fibrillated TFE containing co-coagulated polymers, (4) mixtures of (1 ), (2) and (3).OE-32. Any OE above including an electrode polymer comprising fibrillated, TFE containing polymers,OE-33. Any OE above including an electrode polymer comprising fibrillated TFE containing copolymers.OE-34. Any OE above including an electrode polymer comprising fibrillated TFE co-coagulated polymers and an electrochemically reduction inhibiting film(s) comprising a product derived from a voltage initiated mechanism, including but not limited to at least one of decomposition, absorption, assimilation, infusion, incorporation, polymerization, co-polymerization with an electrolyte, other electrolyte additives ,and polymeric electrode components, or co-polymerization with a partially reduced polymer of a polymeric component of the an electrolyte composition comprising, 1 .2 M Li P Fe, EC / DEC (3:7 by volume) and one of (1 ) 1 wt % LiBOB and 4 wt % FEC, (2) 5 to10 wt % LiFSI, (3) 5-10 wt % LiFSI and 4 wt % FEC, (4) 5 wt % LiFSI, (5) 5 wt % LiDFOB, (6) 5 wt % LiBOB or (7) 1 wt % LiDFOB and 4 wt % FEC, and said electrode comprises, consists essentially of, or consist of a material selected from one of graphite, graphene, mesocarbon microbeads (MCMB ), silicon, or SiOxor mixtures thereof, silicon / carbon / graphite composites, SiOx / carbon / graphite composite, lithiated tin oxide, conductive black phosphorus; SnC>2, SnO, nanocomposites containing antimony, oxides of aluminum titanium and molybdenum, and the polymer selected from one of (1 ) at least partially fibrillated or fully fibrillated TFE containing polymers, (3) at least partially fibrillated or fully fibrillated TFE containing copolymers, (4) at least partially fibrillated or fully fibrillated TFE co-coagulated polymers, (5) or mixtures of one of at least partially fibrillated or fully fibrillated TFE containing polymers, copolymers, and co-coagulated polymers.OE-35. A method comprising: a) providing an electrode containing conductive and binder components, b) assessing the neutron / X-ray generated scattering peaks of the components, c) arranging the electrode in a lithium ion battery containing an electrolyte,d) applying a voltage that sweeps across a voltage range, e) assessing the intensity the s neutron / X-ray generated scattering peaks of the electrode components after (d), f) repeating steps (a)-(d) with a stabilizing additive in an electrolyte, and g) selecting a stabilizing additive based on scattering peak intensity wherein the stabilizing additive mixture selected from at least one lithium salt additive comprising and one or more of an oxalate, borate, sulfonyl or sulfonyl imide group and optionally fluorine, or at least one additive mixture containing at least one cyclic additive containing fluorine.OE-36. A method comprising: a) providing an electrode containing conductive and binder components, b) assessing the neutron / X-ray generated scattering peak intensity of the electrode components in an electrolyte with and without a stabilizing additive, and c) selecting a stabilizing additive based on the neutron / X-ray generated scattering peak intensity wherein the stabilizing additive is selected from one of (i) at least one lithium salt additive comprising and one or more of an oxalate, borate, sulfonyl or sulfonyl imide group and optionally fluorine, or (ii) at least one additive (ii) containing at least one unsaturated C=C bond, and at least one cyclic additive containing fluorine, or a combination of two or more of (i), (ii) and (iii), with the proviso that (iii) is included.OE-37. The electrode of OE-2 wherein the polymer is reduced or partially reduced.OE-38. The electrode of any of OE-8-OE-14 wherein the polymer is reduced or partially reduced.OE-39. A film in any of the OE embodiments above wherein the film can comprises one or more layers, each layer independently the same or different chemically, each independently continuous or non-continuous.

[0217] Although certain aspects, embodiments and principals have been described above, it is understood that this description is made only way of example and not as limitation of the scope of the invention or appended claims. The foregoing various aspects, embodiments and principals can be used alone and in combinations with each other.

Claims

CLAIMSWhat is claimed is:1 . A self-supporting electrode comprising, at least a partially fibrillated binder having exposed surfaces, said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C between 0.9 volts to 0.3 volts versus Li / Li+, said electrolyte comprises,■ a non-aqueous electrolyte solvent,■ 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 a C1-C4 alkyl group, preferably the at least one cyclic additive comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC), and■ at least one additional component selected from: (1 ) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and (2) at least one unsaturated C=C bond containing compound comprising 1- propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate excluding VC and VEC.

2. A self-supporting electrode comprising, at least a partially fibrillated binder having exposed surfaces, said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers,at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25° C■ a non-aqueous electrolyte solvent,■ 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 a C1-C4 alkyl group, preferably the at least one cyclic additive comprises a C2 or C3 fluoroalkene carbonate which is unsubstituted or substituted with a C1-C4 alkyl group, most preferably the at least one cyclic additive comprises fluoroethylene carbonate (FEC), and■ at least additional component selected from: (1) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and (2) at least one unsaturated C=C bond containing additive comprising 1 -propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free of vinyl carbonate compounds comprising VC and VEC. said electrode having a reduction peak magnitude between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished by at least 20% relative to that observed using electrodes lacking said at least one binder-electrolyte derived layer.

3. A self-supporting electrode comprising, at least a partially fibrillated binder having exposed surfaces, said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C between 0.9 volts to 0.3 volts versus Li / Li+, said electrolyte comprises:■ a non-aqueous electrolyte solvent, an effective amount of one of LiTFSI, LIDFOB, and LiDFOB, and optionally at least one cyclic additive containing fluorine, preferably a compound containing a C2 or C3 fluoroalkene carbonate, most preferably fluoroethylene carbonate (FEC), said electrode having a reduction peak magnitude between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement that is diminished by at least 20% relative to that observed using electrodes lacking the binder-electrolyte derived layer.

4. The electrode of claim 2 or claim 3, wherein the reduction peak magnitude versus Li / Li+ in a cyclic voltammetry measurement is diminished by one of 30, 40%, 50%, 60% or more relative to an electrode without said at least one binderelectrolyte derived layer.

5. The electrode claim 1 wherein said electrolyte consists essentially of a nonaqueous electrolyte solvent, an effective amount of at least one cyclic C2 or C3 fluoroalkene carbonate, at least one lithium salt comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide group and optionally fluorine.

6. The electrode claim 2 wherein said electrolyte consists essentially of a nonaqueous electrolyte solvent, an effective amount of at least one cyclic C2 or C3 fluoroalkene carbonate, at least one lithium salt comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide group and optionally fluorine.

7. The electrode of claim 1 wherein the cyclic carbonate containing fluorine is selected from fluoroethylene carbonate (FEC), 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).

8. The electrode of claim 3 wherein the cyclic carbonate containing fluorine is selected from fluoroethylene carbonate (FEC), 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).

9. The electrode of claim 1 wherein the cyclic carbonate containing fluorine comprises at least fluoroethylene carbonate (FEC).

10. The electrode of claim 2 wherein the cyclic carbonate containing fluorine 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 LiDFOB13. The electrode of any of claims 12 or 13 further comprises a cyclic fluorocarbonate selected from fluoroethylene carbonate (FEC), 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).

14. The electrode of any of claim 1-3 wherein the polymeric binder comprises one of: a co-coagulated composition containing 95 wt% PTFE1 and 10 wt% PFA1 , a modified tetrafluoroethylene polymer, containing 0.018 wt% of copolymerized PFBE (perfluorobutyl ethylene) and 0.016 wt% HFP (hexafluoropropylene) modifiers, having a melt creep viscosity of 1 .5 x 1011poise, a co-coagulated composition containing 95 wt% PTFE2 and 5 wt% PFA1 , a co-coagulated composition containing 95 wt% PTFE2 and 5 wt% PFA1 , a co-coagulated composition containing >95 wt% PTFE and up to 5 wt% FKM,a modified tetrafluoroethylene polymer, containing 0.128 wt% of copolymerized PPVE (perfluoro(propyl vinyl ether) as modifier, having a melt creep viscosity of 1 .47 x 1010poise, a co-coagulated composition containing 95 wt% PTFE3 and 5 wt% PFA1 , a co-coagulated composition containing 95 wt% PTFE3 and 10 wt% PFA1 , a co-coagulated product containing 95 wt% PTFE3 and 5 wt% FKM1 , or> a modified tetrafluoroethylene polymer, containing 0.038 wt% of copolymerized PFBE (perfluorobutyl ethylene) as modifier, having a melt creep viscosity of 9.16 x 1010poise, wherein■ PFA1 is copolymer of tetrafluoroethylene and perfluoro(propyl vinyl ether) (PPVE), PPVE content 4 weight percent, having a melt flow rate of 15 g / 10 minutes, and having total carboxylic acid type unstable ends content of about 200 per 106C atoms,■ FKM is copolymer of vinylidene fluoride and hexafluoropropylene (HFP), HFP content 40 weight percent and having a Mooney viscosity of 114 MU, measured at 121 C,■ PTFE1 is tetrafluoroethylene homopolymer having a melt creep viscosity of 4.0 x 1011poise,■ PTFE2 modified tetrafluoroethylene polymer, containing 0.018 wt% of copolymerized PFBE (perfluorobutyl ethylene) and 0.016 wt% HFP (hexafluoropropylene) modifiers, having a melt creep viscosity of 1 .5 x 1011poise),■ PTFE3 is modified tetrafluoroethylene polymer, containing 0.128 wt% of copolymerized PPVE (perfluoro(propyl vinyl ether) as modifier and a melt creep viscosity of 1 .47 x 1010poise, wherein about” is defined to include one of ± 1 %, ± 2%, or ± 3% up to the stated value.

15. An electrochemical device comprising the electrode of any of the preceding claims.

16. A secondary lithium ion battery comprising the electrode of any of the preceding claims.

17. A battery including, an anode electrode bearing a film, a cathode, and an electrolyte, wherein the anode electrode bearing the film comprises the electrode of claim 1.

18. A battery including, an anode electrode bearing a film, a cathode, and an electrolyte, wherein the anode electrode bearing a film comprises the electrode of claim 2.

19. A battery including, an anode electrode bearing a film, a cathode, and an electrolyte, wherein the anode electrode bearing a film comprises the electrode of claim 3.

20. A process comprising, providing at least a partially fibrillated binder having exposed surfaces said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, contacting the electrode of (a) with an electrolyte, said electrolyte comprises said electrolyte comprises:■ a non-aqueous electrolyte solvent,■ an effective amount of at least one cyclic additive containing fluorine, preferably a cyclic fluorocarbon additive, more preferably a C2 or C3 fluoroalkene carbonate, most preferably fluoroethylene carbonate (FEC), and■ at least one additional component selected from: at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and at least one unsaturated C=C bond containing compound comprising 1 -propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free of vinyl carbonate compounds.applying a sweep between or across a voltage range and forming a reduction inhibiting film or deposit on the exposed surfaces of the electrode, and diminishing the magnitude of the reduction peak using the electrode between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished by at least 20% relative to a 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 process of claim 20 wherein the magnitude of the reduction peak between 0.9 V versus 0.3 V vs. Li / Li+is diminished by one of 30%, 40%, 50%, 60% or more relative to an electrode without said film.

22. The process of claim 21 wherein the sweep between or across a voltage range is selected from one of 1 .0 V to 0.6 V, 1 .0 V to 0 V, 1.5 V to 0.6V, 1 .5 V to 0 V, or 2.0V to 0.6V versus Li / Li+23. A process for diminishing the electrochemical reduction of at least a partially fibrillated binder having exposed surfaces comprising PTFE or TFE containing copolymers and a TFE content of at least 90 wt. %, comprising contacting an electrode formed with the polymer and an electrolyte comprising an effective amount of fluoroethylene carbonate (FEC) and additional component selected from: (1 ) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and (2) at least one unsaturated C=C bond containing compound comprising 1 -propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding vinyl carbonate compounds, wherein the electrode is placed in a secondary lithium ion battery with a counter electrode and at least one sweep is performed where the anode potential is varied from at least 1.0 V vs. Li / Li+or higher to at least 0.6 V vs Li / Li+, with a lower limit of 0 V vs Li / Li+when a graphite electrode is used, the electrochemical reduction of the polymer and the electrolyte is diminished by at least 20% relative to an electrode with a film produced without the combination of FEC and the additional component.

24. The electrode of any of claims 20-22 wherein electroche ical reduction of the electrode and the electrolyte in a secondary lithium ion battery is diminished by 30%, 40%, 50%, 60% or more.

25. The process of any of claims 20-22, wherein diminution of electrochemical reduction is measured by the ratio of the peak height assigned to the reduction in the region of 0.9 V to 0.3 V (vs. Li / Li+) to the peak height produced without the combination of FEC and the additional component.

26. The electrode of any of claims 1-3 comprising, graphite, conductive carbon and the binder is selected from one of a PTFE homopolymer, TFE co-polymer formed with one of hexafluoropropylene (HFP), perfluoro(alkyl vinyl ether) (PAVE), FEP, perfluoro(ethyl vinyl ether)(PEVE) or perfluoro(propyl vinyl ether)(PPVE) or cocoagulated, wherein the TFE content is at least 95 wt. percent.

27. The electrode of any of claims 1-3 further comprising, one of silicon, silicon oxide, combinations of silicon and silicon oxide, and graphite.

28. The electrode of any of claims 1-3 wherein a fibrillated binder having exposed surfaces comprises first and second polymer, wherein the first polymer is selected from : fluoropolymers having a melt creep viscosity different from that of a second polymer, wherein the second polymer is selected from one of polyolefins, polyesters, polyamides, polyimides, polyaramides, polyacrylates, polyurethanes, polyethers, polyolethers, polyacrylonitriles, polyphosphazenes, polysiloxanes, polysulfides and polysulfones.

29. The electrode of claim 1 wherein the electrolyte composition comprises 1 .2 M LiPFe + EC / DEC (3:7 by volume), and one of: (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 process of claim 2 wherein the electrolyte and electrolyte additives comprises 1.2 M LiPFe + EC / DEC (3:7 by volume) as the electrolyte and one of: (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 of claim 3 wherein the electrolyte composition comprises 1 .2 M LiPFe + EC / DEC (3:7 by volume), and one of: (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 LiPFe + EC / DEC (3:7 by volume), and one of: (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 process of claim 20 wherein the electrolyte and electrolyte additives comprises 1.2 M LiPFe + EC / DEC (3:7 by volume) as the electrolyte and one of: (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 of claim 4 wherein the electrolyte composition comprises 1 .2 M LiPFe + EC / DEC (3:7 by volume), and one of: (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 comprising: a. providing an electrode containing conductive and at least a partially fibrillated TFE binder components, b. assessing a scattering peak intensity of electrode components in an electrolyte with and without a stabilizing additive, and c. selecting a stabilizing additive based on the scattering peak intensity 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 fluoroalkene carbonate, most preferably fluoroethylene carbonate (FEO), and at least additional component selected from: (1) at least one lithium salt additive comprising one or more of an oxalate, borate or sulfonyl group or sulfonyl imide and optionally fluorine, and (2) at least one unsaturated C=C bond containing compound comprising 1 -propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and excluding vinyl carbonate compounds.

37. The electrode of claim 1 wherein the at least one exposed surface layer comprises multiple layers and each layer is independently the same or different chemically, and each layer is independently continuous, non-continuous, fragmented.

38. The electrode of claim 2 wherein the at least one exposed surface layer comprises multiple layers and each layer is independently the same or different chemically, and each layer is independently continuous, non-continuous, fragmented.

39. The electrode of claim 3 wherein the at least one exposed surface layer comprises multiple layers and each layer is independently the same or different chemically, and each layer is independently continuous, non-continuous, fragmented.

40. The electrode of claim 1 wherein the binder surfaces comprise at least one of fibrils, nodes or non-fibrillated components surfaces of the binder.41 . The electrode of claim 2 wherein the binder surfaces comprise at least one of fibrils, nodes or non-fibrillated components surfaces of the binder.

42. The electrode of claim 3 wherein the binder surfaces comprise at least one of fibrils, nodes or non-fibrillated components surfaces of the binder.

43. A self-supporting electrode comprising,> at least a partially fibrillated binder having exposed surfaces said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers, at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C between 0.9 volts to 0.3 volts versus Li / Li+, said electrolyte comprises: at least one unsaturated C=C bond containing additive comprising 1-propene 1 ,3-sultone, maleic anhydride, 2,5-dihyrofuran, allyl ethyl carbonate, allyl methyl carbonate, and allyl phenyl carbonate, and free of vinyl carbonate compounds said electrode having a reduction peak magnitude between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished relative to that observed using electrodes lacking said at least one binder-electrolyte derived layer.

44. A self-supporting electrode comprising,(a) at least a partially fibrillated binder having exposed surfaces said binder selected from at least one of a TFE homopolymer, a TFE copolymer or coagulated first and second different TFE copolymers,(b) at least one binder-electrolyte derived layer on said exposed surfaces which diminishes the reduction peak magnitude using an electrode in a cyclic voltammetry measurement at 25°C between 0.9 volts to 0.3 volts versus Li / Li+, said electrolyte comprises a non-aqueous electrolyte solvent and an effective amount maleic anhydride, said electrode having a reduction peak magnitude between at 0.9 volts to 0.3 volts versus Li / Li+ in a cyclic voltammetry measurement is diminished by at least 20% relative to that observed using electrodes lacking said at least one binder-electrolyte derived layer.

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