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• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/621—Binders
  • H01M4/622—Binders being polymers
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08L15/00—Compositions of rubber derivatives
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • H—ELECTRICITY
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
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  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
  • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
  • H01M10/0562—Solid materials
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  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
  • H01M4/624—Electric conductive fillers
  • H01M4/625—Carbon or graphite
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/027—Negative electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0068—Solid electrolytes inorganic
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• TECHNICAL FIELD This application relates to the field of polymers and their use in electrochemical applications. More particularly, the present application relates to the field of polymer binders, to electrode materials comprising them, to their production methods and to their use in electrochemical cells, in particular in so-called all-solid-state batteries. STATE OF THE ART
• An ideal all-solid-state electrochemical system would consist of a negative electrode, a solid electrolyte, and a composite positive electrode composed of an electrochemically active material, the solid electrolyte, and possibly a conductive material. electronic. All of which can form a monolithic whole.
• One of the key elements of an all-solid-state electrochemical system is the dispersion of each of its constituents. Indeed, the solid elements may tend to agglomerate during the mixing step with the binder, thus making the electrode material non-homogeneous.
• the strategies employed to solve this problem one finds the encapsulation of the particles of the various constituents of the system with coating materials allowing a better dispersion of these.
• These Dispersion problems can also be reduced significantly through the use of binders, additives or dispersion media resulting in better particle dispersion.
• Polymers based on norbornene have been described as additives in the PCT patent application published under the number WO2020/061710 (Daigle et al.), these being added to a polymer binder.
• Polynorbornenes are added, for example, in order to suppress or reduce parasitic reactions such as the formation of lithium fluoride (LiF) and hydrofluoric acid (HF) resulting from the degradation of carbon-fluorine (C-F) bonds.
• Korean patent published under number KR 10-2193945 and PCT patent application published under number WO2019/004714 describe a method for manufacturing a solid electrolyte film comprising a sulfide-based solid electrolyte and a composite electrode making it possible to improve the properties of dispersion, density and ionic conductivity between the particles of solid electrolyte and between the particles of solid electrolyte and the particles of active material by crystallization from an amorphous to crystalline state.
• a copolymer based on norbornene is used, in particular poly(ethylene-co-propylene-co-5-methylene-2-norbornene (PEPMNB).
• the present technology relates to a binder composition
• a binder composition comprising a blend comprising a polybutadiene-based polymer and a polynorbornene-based polymer comprising norbornene-based monomer units derived from the polymerization of a compound of Formula I:
• R 1 and R 2 are independently and at each occurrence chosen from a hydrogen atom, a carboxyl group (-COOH), a sulphonic acid group (-SO 3 H), a hydroxyl group (-OH), a fluorine atom and a chlorine atom.
• the polynorbornene-based polymer is a polymer of
• R 1 and R 2 are as defined herein, and n is a natural integer chosen so that the weight-average molecular weight of the polymer of Formula II is between approximately 10,000 g/mol and approximately 100,000 g/mol, upper and lower bounds included.
• the weight average molecular weight of the polymer of Formula II is between about 12,000 g/mol and about 85,000 g/mol, or between about 15,000 g/mol and about 75,000 g/mol. , or between approximately 20,000 g/mol and approximately 65,000 g/mol, or between approximately 25,000 g/mol and approximately 55,000 g/mol, or between approximately 25,000 g/mol and approximately 50,000 g/mol, upper and lower limits included.
• R 1 and R 2 are independently and at each occurrence chosen from a hydrogen atom and a —COOH group. According to one example, R 1 is a —COOH group and R 2 is a hydrogen atom. According to another example, R 1 and R 2 are both —COOH groups.
• the polybutadiene-based polymer is polybutadiene. In another embodiment, the polybutadiene-based polymer is selected from epoxidized polybutadienes. According to one example, the epoxidized polybutadiene comprises repeating units of Formulas III, IV and V: and two terminal hydroxyl groups.
• the epoxidized polybutadiene is of Formula VI: wherein, m is a whole number chosen such that the weight average molecular weight of the epoxidized polybutadiene of Formula VI is between about 1000 g/mol and about 1500 g/mol, upper and lower limits inclusive; and the epoxy equivalent weight is between about 100 g/mol and about 600 g/mol, upper and lower limits inclusive.
• the epoxidized polybutadiene is a Poly bd MC 600E resin having a weight-average molecular weight of about 1300 g/mol and an epoxy equivalent weight of between about 400 g/mol and about 500 g/mol. , upper and lower bounds included.
• the epoxidized polybutadiene is a Poly bd MC 605E resin having a weight-average molecular weight of approximately 1300 g/mol and an equivalent weight of epoxide between approximately 260 g/mol and approximately 330 g/mol, upper and lower limits included.
• the polybutadiene-based polymer: polynorbornene-based polymer weight ratio ranges from about 6:1 to about 2:3, upper and lower bounds inclusive.
• the weight ratio is in the range of about 5.5:1 to about 2:3, or about 5:1 to about 2:3, or about 4.5: 1 to about 2:3, or ranging from about 4:1 to about 2:3, or ranging from about 6:1 to about 1:1, or ranging from about 5.5:1 to about 1:1 , or ranging from about 5:1 to about 1:1 , or ranging from about 4.5:1 to about 1:1 , or ranging from about 4:1 to about 1:1 , upper and lower limits included .
• the weight ratio is comprised in the interval going from approximately 4:1 to approximately 1:1, upper and lower limits included.
• the present technology relates to a binder comprising a binder composition as defined herein.
• the binder is used in an electrode material.
• the present technology relates to an electrode material comprising an electrochemically active material and a binder as defined herein.
• the electrochemically active material is selected from metal oxide, metal sulfide, metal oxysulfide, metal phosphate, metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, metal halide of metal, a metal fluoride, sulphur, selenium and a combination of at least two of these.
• the metal of the electrochemically active material is chosen from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and a combination of at least two of these.
• the electrochemically active material further comprises an alkali or alkaline-earth metal chosen from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).
• the electrochemically active material is chosen from a non-alkaline or non-alkaline-earth metal, an intermetallic compound, a metal oxide, a metal nitride, a metal phosphide, a metal phosphate, a metal halide, metal fluoride, metal sulfide, metal oxysulfide, carbon, silicon (Si), a silicon-carbon composite (Si-C), a silicon oxide (SiO x ), a silicon oxide-carbon composite (SiO x -C), tin (Sn), a tin composite - carbon (Sn-C), a tin oxide (SnO x ), a tin oxide-carbon composite (SnO x -C), and a combination of at least two of these.
• the electrochemically active material further comprises a doping element.
• the electrochemically active material is in the form of particles.
• the electrochemically material particles further comprise an encapsulating material.
• the coating material is chosen from LhSiOs, LUTisOia, LiTaOs, UAIO2, LhO-ZrOa, LiNbOs, other similar materials and a combination of at least two of these.
• the coating material is an electronically conductive material.
• the electrode material further comprises an electronically conductive material.
• the electronic conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and a combination at least two of these.
• the surface of said electronically conductive material is grafted with at least one aryl group of Formula VII:
• FG is a hydrophilic functional group; and n is a natural number ranging from 1 to 5, preferably n ranging from 1 to 3, preferably n is 1 or 2, or more preferably n is 1.
• the hydrophilic functional group is a carboxylic acid or sulphonic acid functional group.
• the aryl group of Formula VII is p-benzoic acid or p-benzenesulfonic acid.
• the electrode material further includes an additive.
• the additive is chosen from ionic conductive materials, inorganic particles, glass or glass-ceramic particles, ceramic particles, nano-ceramics, salts and a combination of at least two of these.
• the additive comprises ceramic, glass or glass-ceramic particles based on fluoride, phosphide, sulphide, oxysulphide or oxide.
• the additive is chosen from compounds of the LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite type, oxides, sulphides, oxysulphides, phosphides, fluorides, in crystalline form and/or amorphous, and a combination of two or more thereof.
• the additive is chosen from inorganic compounds of formulas MLZO (for example, M 7 La 3 Zr 2 0i 2 , M (7-a) La 3 Zr 2 Al b Oi 2 , M (7.
• M a GebPcSd such as MioGeP2S-12
• MGPSO e.g., M a Ge b P c S d O e
• MSiPS for example, M a Si b P c S d such as M 10 S1P 2 S 12
• MSiPSO e.g., M a Si b P c S d O e
• MSnPS for example, M a Sn b P c S d such as MioSnP 2 Si 2
• MSnPSO eg, M a Sn b P c S d O e
• MPS for example, M a P b S c such as M 7 P 3 S 11
• MPSO e.g., M a P b S c O d
• MZPS e.g., M a Zn b P c S d
• MZPSO e.g., M a Zn b P c S d
• M is an alkali metal ion, an alkaline earth metal ion or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;
• X is selected from F, Cl, Br, I or a combination of at least two of these;
• a, b, c, d, e and f are numbers other than zero and are independently in each formula selected to achieve electroneutrality;
• v, w, x, y and z are non-zero numbers and are independently in each formula selected to yield a stable compound.
• the additive is chosen from inorganic compounds of argyrodite type of formula LÎ 6 PS 5 X in which X is Cl, Br, I or a combination of at least two of these.
• the additive is LI 6 PS 5 CI.
• the present technology relates to an electrode comprising the electrode material as defined herein on a current collector. According to another aspect, the present technology relates to a self-supporting electrode comprising the electrode material as defined herein.
• the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, in which at least one of the positive electrode or the negative electrode is as defined herein or comprises an electrode material as defined herein.
• the electrolyte is a liquid electrolyte comprising a salt in a solvent.
• the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.
• the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.
• the electrolyte is a polymer-ceramic hybrid solid electrolyte.
• the electrolyte comprises an inorganic solid electrolyte material.
• the inorganic solid electrolyte material comprises ceramic, glass or glass-ceramic particles based on fluoride, phosphide, sulphide, oxysulphide or oxide.
• the electrolyte material inorganic solid is chosen from compounds of the LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites type, oxides, sulphides, oxysulphides, phosphides, fluorides, in crystalline and/or amorphous form, and a combination of at least two of these.
• M is an alkali metal ion, an alkaline earth metal ion or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;
• the inorganic solid electrolyte material is chosen from inorganic compounds of the argyrodite type of formula LÎ 6 PS 5 X in which X is Cl, Br, I or a combination of at least two of these. this.
• the inorganic solid electrolyte material is LI 6 PS 5 CI.
• the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined here.
• the electrochemical accumulator is a battery chosen from among a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, a magnesium-ion battery. In another embodiment, the electrochemical accumulator is a so-called all-solid battery.
• Figure 1 shows in (A) an image by SEM of Film 1, and in (B) the corresponding image of cartography by EDS allowing the analysis of the distribution of the elements Ni and S, as described in Example 4 Scale bars represent 300 ⁇ m and 100 ⁇ m respectively.
• Figure 2 shows in (A) an SEM image of Film 2, and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of the elements Ni and S, as described in Example 4 Scale bars represent 100 ⁇ m.
• Figure 3 shows in (A) an SEM image of Film 3, and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of the elements Ni and S, as described in Example 4 Scale bars represent 100 ⁇ m.
• Figure 4 shows in (A) an SEM image of Film 4, and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of the elements Ni and S, as described in Example 4 Scale bars represent 100 ⁇ m.
• Figure 5 shows in (A) an SEM image of Film 5, and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of the elements Ni and S, as described in Example 4 Scale bars represent 100 ⁇ m.
• Figure 6 shows in (A) an SEM image of Film 7 allowing the different layers of the film to be observed, and in (B) an SEM image seen from above of this same film, as described in Example 4. Scale bars represent 100 ⁇ m.
• Figure 7 shows in (A) an SEM image of Film 8 allowing the different layers of the film to be observed, and in (B) an SEM image seen from above of this same film, as described in Example 4. Scale bars represent 100 ⁇ m.
• Figure 8 shows in (A) an SEM image of Film 9 allowing the different layers of the film to be observed, and in (B) an SEM image seen from above of this same film, as described in Example 4. Scale bars represent 100 ⁇ m.
• Figure 9 shows a graph of discharge capacity (mAh/g) and coulombic efficiency (%) versus number of cycles for Cell 1 ( ⁇ ) and Cell 2 (A), as described in Example 5(b).
• Figure 10 shows a graph of average charge and discharge potential (V) versus number of cycles for Cell 1 ( ⁇ ) and Cell 2 (A), as described in Example 5(b).
• Figure 11 shows a graph of discharge capacity (mAh/g) and coulombic efficiency (%) versus number of cycles for Cell 3 ( ⁇ ), Cell 4 ( ) and Cell 5 ( A), as described in Example 5(b).
• Figure 12 shows a graph of average charge and discharge potential (V) versus number of cycles for Cell 3 ( ⁇ ), Cell 4 ( ), and Cell 5 (A), as described in Figure 12. 'Example 5(b).
• Figure 13 shows in (A) a plot of discharge capacity and coulombic efficiency (%) versus number of cycles for Cell 6 ( ⁇ ), Cell 7 (A), Cell 8 ( ), Cell 9 (T) and Cell 10 ( ⁇ ), as described in Example 5(b).
• Figure 14 shows a graph of average charge and discharge potential (V) versus number of cycles for Cell 6 ( ⁇ ), Cell 7 (A), Cell 8 ( ), Cell 9 (T ) and Cell 10 as described in Example 5(b).
• derived monomer units and equivalent terms, as used herein, refer to repeating polymer units obtained from the polymerization of a polymerizable monomer.
• aryl refers to substituted or unsubstituted aromatic rings, the contributing atoms may form one ring or a plurality of fused rings.
• Representative aryl groups include groups with 6 to 14 ring members.
• aryl can include phenyl, naphthyl, etc.
• the aromatic ring can be substituted at one or more positions of the ring with, for example, a carboxyl (-COOH) or sulphonic acid (-SO 3 H) group, an amine group, and other similar groups.
• hydrophilic functional group designates functional groups attracted by water molecules.
• the hydrophilic functional groups can generally be charged and/or capable of forming hydrogen bridges.
• Non-limiting examples of hydrophilic functional groups include hydroxyl, carboxyl, sulfonic acid, phosphonic acid, amine, amide and other similar groups. The term further encompasses the salts of these groups, where appropriate.
• self-supporting electrode refers to an electrode without a metallic current collector.
• the chemical structures described here are drawn according to the conventions of the field. Also, when an atom, such as a carbon atom, as drawn appears to include an incomplete valence, then the valence is assumed to be satisfied by one or more hydrogen atoms even though they are not explicitly drawn.
• the present technology relates to an electrode binder comprising a mixture of polymers, more specifically an electrode binder comprising a mixture of polymers for use in so-called all-solid electrochemical systems.
• an electrode binder comprising a mixture including a polybutadiene-based polymer and a polynorbornene-based polymer comprising norbornene-based monomer units derived from the polymerization of a compound of Formula I:
• R 1 and R 2 are independently and at each occurrence chosen from a hydrogen atom, a carboxyl group (-COOH), a sulphonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom and a chlorine atom.
• at least one of R 1 or R 2 is chosen from -COOH, -SO 3 H -OH, F, and Cl, which means that at least one of R 1 or R 2 is different from a hydrogen atom.
• R 1 is a —COOH group and R 2 is a hydrogen atom.
• At least one of R 1 or R 2 is a —COOH group and the norbornene-based monomer units are norbornene-based monomer units functionalized with a carboxylic acid.
• R 1 is a —COOH group and R 2 is a hydrogen atom.
• R 1 and R 2 are both —COOH groups.
• the present technology also relates to an electrode binder comprising a mixture including a polybutadiene-based polymer and a polynorbornene-based polymer of Formula II:
• R 1 and R 2 are as defined above, and n is a natural number chosen so that the weight-average molecular weight of the polymer of Formula II is between approximately 10,000 g/mol and approximately 100,000 g/mol as as determined by gel permeation chromatography (GPC), upper and lower limits included.
• the mass average molecular weight of the polynorbornene-based polymer of Formula II is between about 12,000 g/mol and about 85,000 g/mol, or between about 15,000 g/mol and about 75,000 g/mol.
• R 1 and R 2 are —COOH groups.
• the polymer based on polynorbornene is of Formula II(a): in which,
• R 2 and n are as defined previously.
• polymer based on polynorbornene is of Formula 11(b):
• the polymer based on the polynorbornene of Formulas II, 11(a) or 11(b) is a homopolymer.
• the polymerization of a monomer based on norbornene of Formula I can be carried out by all known and compatible polymerization methods.
• the polymerization of the compound of Formula I can be carried out by the synthetic process described by Commarieu, B. et al. (Commarieu, Basile, et al. "Ultrahigh T g Epoxy Thermosets Based on Insertion Polynorbornenes", Macromolecules, 49.3 (2016): 920-925).
• the polymerization of the compound of Formula I can also be carried out by an addition polymerization process.
• polynorbornene-based polymers produced by an addition polymerization process can be substantially stable under severe conditions (eg, acidic and basic conditions). Addition polymerization of polynorbornene-based polymers can be performed using inexpensive norbornene-based monomers.
• the glass transition temperature (T g ) obtained with polynorbornene-based polymers produced by this polymerization route can be at or above about 300°C, for example, as high as 350°C.
• the polybutadiene-based polymer may be characterized by substantially higher elasticity or flexibility and/or a substantially lower glass transition temperature (T v ) than the polynorbornene-based polymer of Formulas II , ll(a) or ll(b).
• the polybutadiene-based polymer can be polybutadiene.
• the polybutadiene-based polymer can be functionalized polybutadiene or a polymer derived from polybutadiene.
• functionalized polybutadiene or polymer derived from polybutadiene may be characterized by substantially higher elasticity or flexibility, and/or by substantially lower glass transition temperature (T v ) and /or can improve the mechanical or cohesive properties of the electrode binder.
• the polymer based on polybutadiene is chosen from epoxidized polybutadienes, for example epoxidized polybutadienes having reactive terminal groups.
• the reactive terminal groups can be hydroxyl groups.
• the epoxidized polybutadiene can comprise repeating units of Formulas III, IV and V:
• the mass average molecular weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V can be between approximately 1000 g/mol and approximately 1500 g/mol as determined by GPC, upper limits and lower included.
• the epoxide equivalent weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V is between about 100 g/mol and about 600 g/mol as determined by GPC, upper and lower limits included .
• the epoxy equivalent weight corresponds to the mass of resin which contains 1 mole of epoxide functional groups.
• the epoxidized polybutadiene is of Formula VI: wherein, m is a whole number chosen such that the mass average molecular weight of the epoxidized polybutadiene of Formula VI is between about 1000 g/mol and about 1500 g/mol as determined by GPC, upper bounds and bottoms included; and the epoxide equivalent weight is between about 100 g/mol and about 600 g/mol as determined by GPC, upper and lower bounds inclusive.
• the mass average molecular weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V or of the epoxidized polybutadiene of Formula VI is between approximately 1050 g/mol and approximately 1450 g/mol, or between approximately 1100 g/mol and approximately 1400 g/mol, or between approximately 1150 g/mol and approximately 1350 g/mol, or between approximately 1200 g/mol and approximately 1350 g/mol, or between approximately 1250 g/mol and about 1350 g/mol as determined by GPC, upper and lower limits included.
• the mass-average molecular weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V or epoxidized polybutadiene of Formula VI is about 1300 g/mol as determined by GPC.
• the epoxy equivalent weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V or of the epoxidized polybutadiene of Formula VI is between approximately 150 g/mol and approximately 550 g/mol, or between approximately 200 g/mol and about 550 g/mol, or between about 210 g/mol and about 550 g/mol, or between about 260 g/mol and about 500 g/mol as determined by GPC, upper and lower bounds included.
• the equivalent weight of epoxide of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V or of the epoxidized polybutadiene of Formula VI is between approximately 400 g/mol and approximately 500 g/mol, or between about 260 g/mol and about 330 g/mol as determined by GPC, upper and lower limits included.
• the epoxidized polybutadiene of Formula VI is an epoxidized polybutadiene resin having commercial end hydroxyl groups of the Poly bd MC 600E or 605E type marketed by Cray Valley.
• the physico-chemical properties of these resins are presented in Table 1.
• the electrode binder comprises a mixture of polymers comprising at least a first polymer and at least a second polymer.
• the first polymer is the polybutadiene-based polymer and the second polymer is the polynorbornene-based polymer comprising norbornene-based monomer units derived from the polymerization of the compound of Formula I or the polymer of Formula II, ll(a) or ll(b).
• the "first polymer:second polymer” ratio is in the range from about 6:1 to about 2:3, upper and lower bounds inclusive.
• the ratio "first polymer: second polymer” is comprised in the range of about 5.5:1 to about 2:3, or about 5:1 to about 2:3, or about 4.5:1 to about 2:3, or ranging from about 4:1 to about 2:3, or ranging from about 6:1 to about 1:1, or ranging from about 5.5:1 to about 1:1, or ranging from about 5: 1 to about 1:1, or ranging from about 4.5:1 to about 1:1, or ranging from about 4:1 to about 1:1, upper and lower bounds inclusive.
• the “first polymer:second polymer” ratio is comprised in the interval going from approximately 4:1 to approximately 1:1, upper and lower limits included.
• the mixture of polymers of said electrode binder can be dissolved in at least one solvent.
• the solvent can be chosen for its ability to solubilize the polymer mixture and to be efficiently mixed therewith.
• the solvent can be an organic solvent, for example a polar aprotic solvent.
• the solvent can be selected from the group consisting of dichloromethane (DCM), N,N-dimethylformamide (DMF), diethyl carbonate (DEC), N,N-dimethylacetamide (DMAC), N-methyl- 2-pyrrolidone (NMP), dioxolane, dioxane, toluene, benzene, methoxybenzene, benzene derivatives, tetrahydrofuran (THF), and a miscible combination of at least two of these.
• DCM dichloromethane
• DMF N,N-dimethylformamide
• DEC diethyl carbonate
• DMAC N,N-dimethylacetamide
• NMP N-methyl- 2-pyrrolidone
• the solvent is THF, a mixture comprising THF and methoxybenzene, a mixture comprising toluene and THF, a mixture comprising toluene and DEC, a mixture comprising toluene and DMAC, a mixture comprising p-xylene and THF, mixture comprising m-xylene and THF, mixture comprising o-xylene and THF, mixture comprising p-xylene and DEC, mixture comprising m-xylene and DEC, a mixture comprising o-xylene and DEC, or a mixture comprising toluene and methoxybenzene.
• this solvent is preferably removed from the electrode in which the binder is found before it is assembled with other elements of an electrochemical cell.
• the present technology also relates to the use of the electrode binder as herein defined in an electrode material.
• an electrode material comprising an electrode material including an electrochemically active material and an electrode binder as defined herein is also contemplated.
• the electrode material as defined here further includes an electronically conductive material.
• electronically conductive material include a carbon source such as carbon black (e.g. Ketjen TM carbon and Super P TM carbon), acetylene black (eg Shawinigan carbon and Denka TM carbon black), graphite, graphene, carbon fibers (eg gas phase formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs) and a combination of two or more thereof.
• the electronic conductive material if it is present in the electrode material, can be a modified electronic conductive material such as those described in the PCT patent application published under number WO2019/218067 (Delaporte et al .).
• the modified electronic conductor material can be grafted with at least one aryl group of Formula VII:
• FG is a hydrophilic functional group; and n is a natural number in the range from 1 to 5, preferably n is in the range from 1 to 3, preferably n is 1 or 2, and more preferably n is 1.
• hydrophilic functional groups examples include hydroxyl, carboxyl, sulfonic acid, phosphonic acid, amine, amide and other similar groups.
• the hydrophilic functional group is a carboxyl or sulphonic acid functional group.
• Preferred examples of the aryl group of Formula VII include p-benzoic acid and p-benzenesulfonic acid.
• the electronically conductive material is carbon black optionally grafted with at least one aryl group of Formula VII.
• the electronically conductive material can be a mixture comprising at least one modified electronically conductive material.
• a mixture of carbon black grafted with at least one aryl group of Formula VII and carbon fibers for example, gas phase formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (NTCs) or a combination of two or more thereof.
• said electrode material is a positive electrode material and the electrochemically active material is chosen from a metal oxide, a metal sulphide, a metal oxysulphide, a metal phosphate, a metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, metal halide (eg, metal fluoride), sulfur, selenium, and a combination of two or more of these.
• the electrochemically active material is chosen from a metal oxide, a metal sulphide, a metal oxysulphide, a metal phosphate, a metal fluorophosphate, metal oxyfluorophosphate, metal sulfate, metal halide (eg, metal fluoride), sulfur, selenium, and a combination of two or more of these.
• the metal of the electrochemically active material is chosen from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb) and their combinations, when compatible.
• the electrochemically active material may optionally further comprise an alkali or alkaline-earth metal, for example, lithium (Li), sodium (Na), potassium (K) or magnesium (Mg).
• Non-limiting examples of electrochemically active materials include lithium and metal phosphates, complex oxides, such as LiM'PC (where M' is Fe, Ni, Mn, Co, or a combination thereof), UV3O8, V2O5, LiM ⁇ C , LiM”0 2 (where M” is Mn, Co, Ni, or a combination thereof), Li(NiM'”)0 2 (where M'” is Mn, Co, Al, Fe, Cr, Ti, or Zr, or a combination thereof) and combinations thereof, when compatible.
• LiM'PC where M' is Fe, Ni, Mn, Co, or a combination thereof
• UV3O8 V2O5 LiM ⁇ C
• LiM 0 2
• Li(NiM'”)0 2 where M'” is Mn, Co, Al, Fe, Cr, Ti, or Zr, or a combination thereof
• the electrochemically active material is an oxide or a phosphate such as those described above.
• the electrochemically active material is a lithium manganese oxide, in which the manganese may be partially substituted by a second transition metal, such as a lithium nickel manganese cobalt oxide (NMC) .
• the electrochemically active material is lithium iron phosphate.
• the electrochemically active material is a lithium metal phosphate containing manganese such as those described above, for example, the lithium metal phosphate containing manganese is a lithium iron and manganese phosphate (LiMni- x Fe x P0 4 , where x is between 0.2 and 0.5).
• said electrode material is a negative electrode material and the electrochemically active material is chosen from a non-alkaline and non-alkaline-earth metal (for example, indium (In), germanium ( Ge) and bismuth (Bi)), an intermetallic compound (for example, SnSb, TiSnSb, Cu 2 Sb, AlSb, FeSb 2 , FeSn 2 and CoSn 2 ), a metal oxide, a metal nitride, a phosphide of metal, metal phosphate (eg, LiThiPO ⁇ ), metal halide (eg, metal fluoride), metal sulfide, metal oxysulfide, carbon (eg, graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), silicon-carbon composite (Si-C), silicon oxide (SiO x ), silicon oxide-carbon composite (SiO x -C),
• the metal oxide can be chosen from compounds of formula M”” b O c (where M”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and b and c are numbers such that the ratio c:b is in the range from 2 to 3) (for example, M0O 3 , M0O 2 , M0S 2 , V 2 O 5 , and TiNb 2 0 7 ), spinel oxides (for example, N1C0 2 O 4 , ZhOq 2 q 4 , MnCo 2 0 4 , CUC0 2 O 4 , and CoFe 2 Ü 4 ) and LiM””O (where M'” ” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination of two or more of these) (for example, a lithium titanate (such as Li 4 Ti 5 Oi 2 ) or a lithium molybdenum oxide (such as
• the electrochemically active material can optionally be doped with other elements included in smaller quantities, for example to modulate or optimize its electrochemical properties.
• the electrochemically active material can be doped by the partial substitution of the metal by other ions.
• the electrochemically active material can be doped with a transition metal (e.g. Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn or Y) and/or a metal other than a transition metal (for example, Mg, Al or Sb).
• a transition metal e.g. Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn or Y
• a metal other than a transition metal for example, Mg, Al or Sb
• the electrochemically active material can be in the form of particles (eg, microparticles and/or nanoparticles) which can be freshly formed or from a commercial source.
• the electrochemically active material can be in the form of particles coated with a layer of coating material in a configuration of the core-coating type (core-shell).
• the potting material may be an electronically conductive material, for example a conductive carbon potting.
• the conductive carbon layer can also optionally be grafted with at least one aryl group of Formula VII.
• the coating material can make it possible to substantially reduce the interfacial reactions at the interface between the electrochemically active material and an electrolyte, for example, a solid electrolyte, and in particular, a solid electrolyte of the ceramic type based on sulphide (for example, based on LÎ 6 PS 5 CI).
• the coating material can be chosen from LhSiOs, LUTisO ⁇ , LiTaOs, UAIO2, LÎ 2 0-Zr0 2 , LiNb0 3 their combinations, when compatible, and other similar materials.
• the coating material comprises LiNbOs.
• the electrode material as defined here further includes an additive.
• the additive is chosen from ionic conductive materials, inorganic particles, glass or glass-ceramic particles, ceramic particles, including nanoceramics (for example, Al 2 O 3 , T1O 2 , S1O 2 and other similar compounds), salts (eg lithium salts) and a combination of two or more of these.
• the additive may be an ionic conductor chosen from compounds of the LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite type, oxides, sulphides, sulfur halides, phosphates, thio-phosphates, crystalline and/or amorphous form, and a combination of at least two of these.
• the additive if it is present in the electrode material, can be ceramic, glass or glass-ceramic particles of crystalline and/or amorphous form.
• the ceramic, glass or glass-ceramic particles can be based on fluoride, phosphide, sulphide, oxysulphide, oxide, or a combination of at least two of these.
• Non-limiting examples of ceramic, glass or glass-ceramic particles include inorganic compounds of the formulas MLZO (e.g., M7La3Zr2Oi2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a) La 3 Zr (2-b) Ta b Oi 2 , and M ( 7- a) La 3 Zr ( 2- b) Nb b Oi2); MLTaO (e.g., M7La 3 Ta 2 Oi2, M 5 La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (eg, M7La3Sn20i2); MAGP (e.g.
• MLZO e.g., M7La3Zr2Oi2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a
• M is an alkali metal ion, an alkaline earth metal ion or a combination thereof, and wherein when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality;
• X is selected from F, Cl, Br, I or a combination of at least two of these; a, b, c, d, e and f are numbers other than zero and are independently in each formula selected to achieve electroneutrality; and v, w, x, y and z are non-zero numbers and are independently in each formula selected to yield a stable compound.
• M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and a combination of two or more of these.
• M comprises Li and may further comprise at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and a combination of at least two of these.
• M comprises Na, K, Mg or a combination of at least two of these.
• the additive if present in the electrode material, may be sulfide-based ceramic particles, for example, argyrodite-type ceramic particles of the formula LÎ 6 PS 5 X (where X is Cl, Br, I or a combination of two or more thereof).
• the additive is argyrodite LÎ 6 PS 5 CI.
• the method of preparing the electrode material as herein defined further includes the use of a solvent, e.g., an organic solvent.
• a solvent e.g., an organic solvent.
• the solvent can provide an optimum viscosity for coating the electrode material, around 10,000 cP, and can be substantially removed in a post-coating drying step.
• the solvent can be THF or methoxybenzene (or anisole).
• the present technology also relates to an electrode comprising an electrode material as defined herein.
• the electrode can be on a collector of current (for example, aluminum or copper foil).
• the electrode can be self-supporting.
• the present technology also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the negative electrode or the positive electrode is as defined herein.
• the negative electrode is as defined here.
• the electrochemically material of the negative electrode can be chosen for its electrochemical compatibility with the different elements of the electrochemical cell as defined here.
• the electrochemically material of the negative electrode material may possess a substantially lower oxidation-reduction potential than that of the electrochemically active material of the positive electrode.
• the positive electrode is as defined here and the negative electrode includes an electrochemically active material chosen from among all known compatible electrochemically active materials.
• the electrochemically active material of the negative electrode can be chosen for its electrochemical compatibility with the different elements of the electrochemical cell as defined here.
• electrochemically active negative electrode materials include alkali metals, alkaline earth metals, alloys comprising at least one alkali or alkaline earth metal, non-alkaline and non-alkaline earth metals (e.g.
• the electrochemically active material of the negative electrode may be in the form of a film having a thickness in the range of from about 5 ⁇ m to about 500 ⁇ m and preferably in the range of from about 10 ⁇ m to about 10 ⁇ m. about 100 pm, upper and lower bounds included.
• the electrochemically active material of the negative electrode can comprise a film of metallic lithium or of an alloy including metallic lithium.
• the positive electrode can be pre-lithiated and the negative electrode can be initially (ie before the cycling of the electrochemical cell) substantially or completely free of lithium.
• the negative electrode can be lithiated in situ during the cycling of said electrochemical cell, in particular during the first charge.
• metallic lithium can be deposited in situ on the current collector (for example, a copper current collector) during the cycling of the electrochemical cell, in particular during the first charge.
• an alloy including metallic lithium can be generated at the surface of a current collector (for example, an aluminum current collector) during the cycling of the electrochemical cell, in particular during the first charge. It is understood that the negative electrode can be generated in situ during the cycling of the electrochemical cell, in particular during the first charge.
• the positive electrode and the negative electrode are both as defined here.
• the electrolyte can be chosen for its compatibility with the various elements of the electrochemical cell. Any type of compatible electrolyte is envisaged.
• the electrolyte is a liquid electrolyte comprising a salt in a solvent.
• the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.
• the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.
• the electrolyte comprises an inorganic solid electrolyte material, for example, the electrolyte can be a ceramic type solid electrolyte.
• the electrolyte is a polymer-ceramic hybrid solid electrolyte.
• the salt if present in the electrolyte, can be an ionic salt, such as a lithium salt.
• lithium salts include lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), 2-trifluoromethyl-4,5 -lithium dicyano-imidazolate (LiTDI), lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA), lithium bis(pentafluoroethylsulfonyl)imide (LiBETI), lithium difluorophosphate (LiDFP), lithium tetrafluoroborate (L1BF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (UNO3), lithium chloride (LiCI), lithium bromide (LiBr), lithium fluor
• LiPFe lithium he
• the solvent if present in the electrolyte, may be a non-aqueous solvent.
• solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); acyclic carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) and dipropyl carbonate (DPC); lactones such as ⁇ -butyrolactone (g-BL) and ⁇ -valerolactone (g-VL); acyclic ethers such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (DEE), ethoxy methoxy ethane (EME), trimethoxymethane and ethylmonoglyme; cyclic ethers such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3
• the electrolyte is a gel electrolyte or a polymer gel electrolyte.
• the gel polymer electrolyte may comprise, for example, a polymer precursor and a salt (for example, a salt as defined above), a solvent (for example, a solvent as defined above) and a polymerization initiator and / or crosslinking, if necessary.
• examples of gel electrolytes include, without limitation, gel electrolytes such as those described in PCT patent applications published under the numbers WO2009/111860 (Zaghib et al.) and WO2004/068610 (Zaghib et al.).
• a gel electrolyte or a liquid electrolyte as defined above can also impregnate a separator such as a polymer separator.
• separators include, without limitation, polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), poly(vinylidene fluoride) (PVDF) and polypropylene-polyethylene-polypropylene (PP) separators. /PE/PP).
• the separator is a commercial polymer separator of the Celgard TM type.
• the electrolyte is a solid polymer electrolyte.
• the solid polymer electrolyte composition can be chosen from all known solid polymer electrolyte compositions and can be chosen for its compatibility with the various elements of an electrochemical cell.
• Solid polymer electrolyte compositions generally comprise a salt as well as one or more solid polar polymer(s), optionally crosslinked.
• Polyether type polymers such as those based on poly(ethylene oxide) (POE)
• POE poly(ethylene oxide)
• the polymer can be cross-linked. Examples of such polymers include branched polymers, for example, star polymers or comb polymers such as those described in the PCT patent application published under number WO2003/063287 (Zaghib et al.).
• the solid polymer electrolyte composition can include a block copolymer composed of at least one lithium ion solvation segment and optionally at least one crosslinkable segment.
• the lithium ion solvation segment is chosen from homo- or copolymers having repeating units of Formula VIII: (CH 2 -CH-0) x -
• R is chosen from a hydrogen atom, and a CiC-ioalkyl group or a -(CH 2 -O-R a R b ) group;
• R a is (CH 2 -CH 2 -0) y ;
• R b is chosen from a hydrogen atom and a CiC-ioalkyl group; x is an integer selected from the range of 10 to 200,000; and y is an integer selected from the range 0 to 10.
• the crosslinkable segment of the copolymer is a polymer segment comprising at least one functional group crosslinkable in a multidimensional manner by irradiation or by heat treatment.
• the electrolyte comprises an ion-conductive inorganic solid electrolyte material and can comprise ceramic, glass or glass-ceramic particles.
• ceramic, glass or glass-ceramic particles based on fluoride, phosphide, sulphide, oxysulphide, oxide, or a combination of at least two of these.
• the electrolyte comprises ceramic, glass or glass-ceramic particles as described previously.
• the electrolyte is a polymer-ceramic hybrid solid electrolyte, and may, for example, comprise particles of inorganic material as defined here, previously dispersed in a solid polymer electrolyte as defined above.
• the polymer-ceramic hybrid solid electrolyte comprises a layer of ceramic electrolyte as defined above between two layers of solid polymer electrolyte as defined above.
• the electrolyte may also optionally include additives such as ionic conductive materials, inorganic particles, glass or ceramic particles as defined above and other additives of the same type.
• the additive may be a dicarbonyl compound such as those described in the PCT patent application published under the number WO2018/116529 (Asakawa et al.).
• the additive can be poly(ethylene-alt-maleic anhydride) (PEMA).
• PEMA poly(ethylene-alt-maleic anhydride)
• the additive can be chosen from all known electrolyte additives and can be chosen for its compatibility with the different elements of the electrochemical cell.
• the additive can be substantially dispersed in the electrolyte.
• the additive may be present in a separate layer.
• the electrode binder comprising a polymer mixture as defined here can significantly improve the dispersion of the various constituents of the material of the positive electrode, in particular of the solid constituents.
• the electrode binder comprising a polymer mixture as defined herein can substantially promote the dispersion of the electrochemically active material, the electronic conductive material and/or the ceramic type solid electrolyte material.
• the R 1 and/or R 2 groups of the polymer based on the polynorbornene of the mixture of polymers of the said binder can be groups which can promote the dispersion of one of these materials.
• carboxyl groups (-COOH) may be groups which can promote the dispersion of one of these materials.
• repulsive interactions linked to the polymer mixture of said material could allow a better dispersion of the constituents of the positive electrode in the dispersion, and this, by the modification or not of the other constituents allowing this type of interactions.
• the repulsive interactions can be pp-type and/or polar interactions.
• the various constituents of the positive electrode material can be modified in order to substantially increase the repulsive interactions with the mixture of polymers of said binder, and thus, to promote their dispersion.
• the various constituents of the positive electrode can be modified by coating them with a coating material encouraging repulsive interactions, for example, p-p type and/or polar interactions.
• at least one of the electrochemically active material, the electronic conductive material and the ceramic-like electrolyte material can be coated with a potting material encouraging repulsive interactions.
• the coating material may comprise at least one branched or linear unsaturated aliphatic hydrocarbon having 10 to 50 carbon atoms and having at least one carbon-carbon double or triple bond.
• such a coating material may be a mixture comprising said unsaturated aliphatic hydrocarbon and an additional component.
• the additional component may be an alkane (eg, an alkane having 10 to 50 carbon atoms) or a mixture comprising an alkane (eg, as defined herein) and a polar solvent (eg, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or a miscible combination of two or more of these).
• the additional component is decane or a mixture comprising decane and tetrahydrofuran.
• a conductive material such as a carbon
• the electrochemical performance of the positive electrode material is not substantially negatively affected by these modifications and their interactions. The phenomena of ionic and electronic conduction can even be favored as well as the electrochemical double layer presenting a better stability.
• the present technology also relates to a battery comprising at least one electrochemical cell as defined here.
• the battery may be a battery primary (battery) or secondary (accumulator).
• the battery is chosen from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, a a magnesium-ion battery, a potassium battery and a potassium-ion battery.
• the battery is a so-called all-solid battery.
• Example 1 Preparation of ceramic particles of the argyrodite type of formula LiePSsCI a) Coating of particles of LiePSsCI with a mixture of heptane and dibutyl ether (50:50 by volume)
• the coating of the LiePSsCI particles was carried out by a method of grinding the particles in a wet way.
• the coating of the LiePSsCI particles was carried out during the wet milling of the particles to reduce the particle size and by using a planetary micromill PULVERISETTE MC 7.
• the coating material comprised a mixture of heptane and dibutyl ether ( 50:50 by volume). 4 g of LiePSsCI particles were placed in an 80 mL zirconium oxide (or zirconia) milling jar. A mixture comprising 13 ml of heptane and 13 ml of anhydrous dibutyl ether (50:50 by volume) as well as grinding balls 2 mm in diameter were added to the jar.
• the LiePSsCI particles and the mixture of heptane and dibutyl ether were combined by grinding at a speed of about 300 rpm for about 7.5 hours to produce LiePSsCI particles coated with the mixture of heptane and ether dibutyl.
• the particles thus obtained were subsequently dried under vacuum at a temperature of about 80°C.
• the coating of the Li 6 PS 5 CI particles was carried out using a PULVERISETTE MC 7 planetary micromill. 4 g of LI 6 PS 5 CI particles were placed in an 80 ml zirconium oxide grinding jar. A mixture comprising 20 ml of anhydrous decane and 7 ml of squalene (75:25 by volume) as well as grinding balls 2 mm in diameter were added to the jar. The LÎ 6 PS 5 CI particles and the decane and squalene mixture were combined by grinding at a speed of about 300 rpm for about 7.5 hours to produce LÎ 6 PS 5 CI particles coated with the decane mixture and squalene. The particles thus obtained were subsequently dried under vacuum at a temperature of about 80°C. c) Coating of LiePS 5 CI particles with a mixture of decane and squalene (90:10 by volume)
• the coating of the LÎ 6 PS 5 CI particles was carried out by a method of grinding the particles and wet mechanosynthesis.
• the coating of the LI 6 PS 5 CI particles was carried out using a PULVERISETTE MC 7 planetary micromill. 4 g of LI 6 PS 5 CI particles were placed in an 80 ml zirconium oxide grinding jar. A mixture of decane and squalene (90:10 by volume) as well as grinding balls 2 mm in diameter were added to the jar. The Ü 6 PS 5 CI particles and the decane and squalene mixture were combined by milling at a speed of about 300 rpm for about 7.5 hours to produce Ü 6 PS 5 CI particles coated with the decane mixture and squalene. The particles thus obtained were subsequently dried under vacuum at a temperature of about 80°C.
• Example 2 - Preparation of the modified electronic conductive material a) Grafting of the particles of electronic conductive material with at least one aryl group of Formula VII
• the coating of particles of electronically conductive material is carried out by a process of particle grinding and wet mechanosynthesis.
• the coating of the carbon black particles is carried out using a PULVERISETTE MC 7 planetary micromill.
• 4 g of carbon black particles are placed in an 80 ml zirconium oxide grinding jar.
• a mixture of anhydrous decane and squalene (75:25 by volume) as well as grinding balls 2 mm in diameter are added to the jar.
• the carbon black particles and the mixture of decane and squalene are combined by grinding at a speed of about 300 rpm for about 7.5 hours to produce particles of carbon black coated with the mixture of decane and squalene.
• the particles thus obtained are subsequently dried under vacuum at a temperature of about 80°C.
• composition of the positive electrode films is shown in Table 2. Table 2. Composition of positive electrode films
• NBR acrylonitrile-butadiene rubber
• SBS styrene-butadiene-styrene
• PB polybutadiene
• PNB polynorbornene of Formula 11(b).
• a positive electrode film 1.55 g of particles of LiNio .6 Mno .2 Coo .2 0 2 (NMC 622) coated with LiNbC>3 from a commercial source having an average diameter d approximately 4 ⁇ m were mixed with 0.40 g of coated LI 6 PS 5 CI particles prepared in Example 1(a) having an average diameter of approximately 200 nm and 0.5 g of carbon black in order to form a mixture of dry powders. The dry powders were mixed for about 10 minutes using a whirlwind (vortex type) mixer.
• a polymer solution was prepared separately by dissolving 0.05 g of acrylonitrile-butadiene rubber (NBR) in 1.187 g of p-xylene.
• the polymer solution was added to the dry powder mixture.
• the mixture thus obtained was mixed for about 5 minutes using a planetary centrifugal mixer (Thinky Mixer).
• An additional quantity of solvent (p-xylene) was added to the mixture in order to reach an optimum viscosity for coating, ie approximately 10,000 cP.
• the suspension thus obtained was coated on an aluminum sheet by a doctor blade coating method. ("doctor-blade coating" in English) to obtain a positive electrode film applied to a current collector.
• the positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours.
• b) Preparation of a positive electrode film (Movie 2)
• NMC 622 particles coated with LiNbOs having an average diameter of about 4 ⁇ m were mixed with 0.40 g of coated ⁇ 6 PS 5 CI particles prepared in Example 1(a) having a diameter medium of about 200 nm and 0.5 g of carbon black to form a mixture of dry powders.
• the dry powders were mixed for about 10 minutes using a whirlwind (vortex type) mixer.
• a polymer solution was prepared separately by dissolving 0.04 g of polybutadiene and 0.01 g of polynorbornene in 0.94 g of THF. The polymer solution was added to the dry powder mixture. The resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer. An additional solvent, methoxybenzene, was added to the mixture in order to reach an optimum viscosity for coating, i.e. approximately 10,000 cP. The suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours. c) Preparation of a positive electrode film (Movie 3)
• a polymer solution was prepared separately by dissolving 0.05 g of SBS in 0.94 g of methoxybenzene.
• the polymer solution was added to the dry powder mixture.
• the resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer.
• An additional amount of methoxybenzene was added to the mixture in order to reach an optimum viscosity for coating, approximately 10,000 cP.
• the suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector.
• the positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours.
• Preparation of positive electrode film (Movie 4)
• NMC 622 particles coated with LiNbOs having an average diameter of about 4 ⁇ m were mixed with 0.40 g of coated LÎ 6 PS 5 CI particles prepared in Example 1(b) having a diameter medium of about 200 nm and 0.5 g of modified carbon black to form a mixture of dry powders.
• the dry powders were mixed for about 10 minutes using a whirlwind (vortex type) mixer.
• a polymer solution was prepared separately by dissolving 0.05 g of polybutadiene in 0.94 g of THF. The polymer solution was added to the dry powder mixture. The resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer. A quantity of methoxybenzene was added to the mixture in order to reach an optimum viscosity for coating, i.e. approximately 10,000 cP. The suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours. e) Preparation of positive electrode film (Movie 5)
• a polymer solution was prepared separately by dissolving 0.04 g of polybutadiene and 0.01 g of polynorbornene in 0.94 g of THF. The polymer solution was added to the dry powder mix. The resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer. A quantity of additional solvent, methoxybenzene, was added to the mixture in order to reach an optimum viscosity for coating, ie approximately 10,000 cP. The suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours. f) Preparation of a positive electrode film (Movie 6)
• NMC 622 particles coated with LiNbOs having an average diameter of approximately 4 ⁇ m were mixed with 0.40 g of coated LÎ 6 PS 5 CI particles prepared in Example 1(c) having a diameter medium of about 200 nm and 0.5 g of modified carbon black to form a mixture of dry powders.
• the dry powders were mixed for about 10 minutes using a whirlwind (vortex type) mixer.
• a polymer solution was prepared separately by dissolving 0.05 g of SBS in 0.94 g of methoxybenzene.
• the polymer solution was added to the dry powder mixture.
• the resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer.
• An additional quantity of methoxybenzene was added to the mixture in order to reach an optimum viscosity for coating, i.e. approximately 10,000 cP.
• the suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector.
• the positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours.
• Preparation of positive electrode film (Movie 7)
• NMC 622 particles coated with LiNbOs having an average diameter of approximately 4 ⁇ m were mixed with 0.40 g of coated LÎ 6 PS 5 CI particles prepared in Example 1(c) having a diameter medium of about 200 nm and 0.5 g of modified carbon black to form a mixture of dry powders.
• the dry powders were mixed for about 10 minutes using a whirlwind (vortex type) mixer.
• a polymer solution was prepared separately by dissolving 0.035 g polybutadiene and 0.015 g polynorbornene in 0.94 g THF.
• the polymer solution was added to the dry powder mixture.
• the resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer.
• An additional quantity of solvent, methoxybenzene, was added to the mixture in order to reach an optimum viscosity for coating, i.e. around 10,000 cP.
• the suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector.
• the positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours.
• a polymer solution was prepared separately by dissolving 0.030 g polybutadiene and 0.020 g polynorbornene in 0.94 g THF. The polymer solution was added to the dry powder mixture. The resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer. An additional quantity of solvent, methoxybenzene, was added to the mixture in order to reach an optimum viscosity for coating, i.e. around 10,000 cP. The suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours. j) Preparation of positive electrode film (Film 10)
• NMC 622 particles coated with LiNbOs having an average diameter of about 4 ⁇ m were mixed with 0.40 g of coated Li 6 PS 5 CI particles prepared in Example 1(c) having a diameter medium of about 200 nm and 0.5 g of modified carbon black to form a mixture of dry powders.
• the dry powders were mixed for about 10 minutes using a whirlwind (vortex type) mixer.
• a polymer solution was prepared separately by dissolving 0.025 g polybutadiene and 0.025 g polynorbornene in 0.94 g THF. The polymer solution was added to the dry powder mixture. The resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer. A quantity of additional solvent, methoxybenzene, was added to the mixture in order to reach an optimum viscosity for coating, ie approximately 10,000 cP. The suspension thus obtained was coated on an aluminum foil by a doctor blade coating method to obtain a positive electrode film applied to a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours.
• Example 4 Characterization of the positive electrode films prepared in Examples 3(a) to 30)
• SEM scanning electron microscope
• EDS energy dispersive X-ray spectrometer
• Figure 1 shows in (A) an image by SEM of the positive electrode film prepared in Example 3(a) (Movie 1), and in (B) the corresponding image of cartography by EDS allowing the analysis of distribution of Ni and S elements. Scale bars represent 300 pm and 100 pm respectively.
• Figure 1(A) the presence of waves on the surface of Film 1, and this, after the step of drying the positive electrode film.
• Figure 1 (B) confirms the presence of nickel (in green) present in the electrochemically active material of the positive electrode (LiNbC>3 - NMC 622) and sulfur (in red) present in the solid electrolyte (LÎ 6 PS 5 CI coated).
• Figure 1 also highlights the presence of sulphide agglomerates on the surface of Film 1. This indicates that the use of a solution of NBR dissolved in p-xylene in the suspension does not make it possible to disperse the particles of solid electrolyte.
• Figure 2 shows in (A) an image by SEM of the positive electrode film prepared in Example 3(b) (Movie 2), and in (B) the corresponding image of mapping by EDS allowing the analysis of distribution of Ni and S elements. Scale bars represent 100 pm.
• Figure 2(A) the absence of waves on the surface of Film 2, after the positive electrode film drying step.
• Figure 2(B) confirms the presence of nickel (in green) and sulfur (in red).
• Figure 2 also highlights the absence of sulphide agglomerates on the surface of Film 2. This indicates that the use of a solution comprising a mixture of polybutadiene and polynorbornene (with -COOH groups) (80:20 by weight) dissolved in THF in the suspension makes it possible to adequately disperse the particles of solid electrolyte.
• Figure 3 shows in (A) an SEM image of the positive electrode film prepared in Example 3(c) (Movie 3), and in (B) the corresponding EDS mapping image allowing analysis of the distribution of Ni and S elements. Scale bars represent 100 ⁇ m.
• Figure 3(A) the presence of a few waves on the surface of Film 3, after the positive electrode film drying step.
• Figure 3(B) confirms the presence of nickel (in green) and sulfur (in red).
• Figure 3 also highlights the presence of sulphide agglomerates on the surface of Film 3. This indicates that the use of a solution of SBS dissolved in methoxybenzene in the suspension does not make it possible to adequately disperse the particles of solid electrolyte.
• Figure 4 shows in (A) an image by SEM of the positive electrode film prepared in Example 3(d) (Movie 4), and in (B) the corresponding image of mapping by EDS allowing the analysis of distribution of Ni and S elements. Scale bars represent 100 pm.
• Figure 4(A) the presence of a few waves on the surface of Film 4, after the positive electrode film drying step.
• Figure 4(B) confirms the presence of nickel (in green) and sulfur (in red).
• Figure 4 also highlights the presence of sulphide agglomerates on the surface of Film 4. This indicates that the use of a solution of polybutadiene dissolved in THF in the suspension does not make it possible to disperse the particles of solid electrolyte in the electrode material.
• Figure 5 shows in (A) an image by SEM of the positive electrode film prepared in Example 3(e) (Movie 5), and in (B) the corresponding image of mapping by EDS allowing the analysis of distribution of Ni and S elements. Scale bars represent 100 pm.
• FIG. 5(A) It is possible to observe in FIG. 5(A) the absence of waves on the surface of Film 5, and this, after the step of drying the positive electrode film.
• Figure 5(B) confirms the presence of nickel (in green) and sulfur (in red).
• Figure 5 also highlights the absence of sulphide agglomerates on the surface of Film 5.
• a solution comprising a mixture of polybutadiene and polynorbornene (with -COOH groups) (80:20 by weight) dissolved in THF in the suspension makes it possible to adequately disperse the particles of solid electrolyte. Without wishing to be bound by theory, this could be related to an effect of using the modified polynorbornene with -COOH groups.
• the dispersion seems to be substantially favored by this type of group and by the carbon bridge linked to the very structure of the polynorbornene. Coating of sulfide particles with molecules having double bonds or triple bonds appears to substantially improve dispersion via tt-p interactions and/or polar repulsions.
• Figures 6 to 8 show in (A) SEM images of the positive electrode films prepared respectively in Examples 3(g) to 3(i) (Movies 7 to 9), and in (B) an SEM image viewed from over those same movies. Scale bars represent 100 ⁇ m.
• Figures 6 to 8 show good dispersion of the components in these positive electrode films. This indicates that the use of a solution comprising a mixture of polybutadiene and polynorbornene (with -COOH groups) dissolved in THF makes it possible to adequately disperse the coated Li 6 PS 5 CI particles and the electronically conductive material by interactions tt-p and polar repulsions.
• Example 5 Electrochemical Properties The electrochemical properties of the positive electrode films prepared in Examples 3(a) through 3(j) were investigated. a) Configurations of electrochemical cells
• the electrochemical cells were assembled according to the following procedure.
• Pellets 10 mm in diameter were taken from the positive electrode films prepared in Examples 3(a) to 3(j).
• Ceramic-like inorganic solid electrolytes based on Li 6 PS 5 CI sulfides were prepared by placing 80 mg of ceramic on the surface of the positive electrode films.
• the positive electrode film pellets including the inorganic solid electrolyte layer were then compressed under a pressure of 2.8 tons using a press. They were then assembled, in a glove box, in CR2032 type button battery boxes facing metallic lithium electrodes 10 mm in diameter on copper current collectors.
• the electrochemical cells were assembled according to the configurations presented in Table 3. Table 3.
• Example 5(a) This example illustrates the electrochemical behavior of the electrochemical cells assembled in Example 5(a).
• the electrochemical cells assembled in Example 5(a) were cycled between 4.3 V and 2.5 V vs Li/Li + .
• Cells 1-5 were cycled at 50°C and Cells 6-10 were cycled at 30°C.
• the formation cycle was carried out at a constant charge and discharge current of C/15.
• four cycles were performed at a constant charge and discharge current of C/10 followed by four cycles at a constant charge and discharge current of C/5.
• the long cycling experiments were performed at a constant charge and discharge current of C/3.
• Figure 9 shows a graph of discharge capacity (mAh/g) and coulombic efficiency (%) as a function of the number of cycles for Cells 1 ( ⁇ ) and 2 (A). It can be seen that there is no substantial difference in capacity retention for Cells 1 and 2. Indeed, the curves are substantially overlapped for the 50°C cycling of Cells 1 and 2.
• Figure 10 shows a graph of average charging and discharging potential (V) as a function of the number of cycles for Cells 1 ( ⁇ ) and 2 (A). It is possible to observe that Cell 2 comprising a mixture of polybutadiene and polynorbornene (with -COOH groups) (80:20 by weight) as a binder makes it possible to obtain a lower polarization during long cycling experiments at a temperature of 50°C and a constant charge and discharge current of C/3. It is also possible to observe a better stability in discharge with the mixture of polybutadiene and polynorbornene (with -COOH groups) (80:20 by weight). Thus, this mixture of polymers ensures better dispersion of the components of the electrode and therefore better ionic and electronic percolation of said components without substantially affecting the charge transfers.
• V average charging and discharging potential
• Figure 11 shows a graph of discharge capacity and coulombic efficiency versus cycle number for Cells 3 ( ⁇ ), 4 (), and 5 (A). It is possible to observe that the capacity retention at a temperature of 50°C and at C/3 is improved when polybutadiene is used in combination with styrene or polynorbornene as a binder. Indeed, Cells 3 and 5 comprising respectively a copolymer of styrene and butadiene (styrene-butadiene-styrene (SBS)) and a mixture of polybutadiene and polynorbornene show an improvement in capacity retention compared to Cell 4 comprising polybutadiene.
• SBS styrene-butadiene-styrene
• Figure 12 shows a graph of the average charge and discharge potential as a function of the number of cycles (linked to Figure 11 ) for Cells 3 ( ⁇ ), 4 ( ⁇ ) and 5 (A). It is possible to observe that Cells 3 and 5 allow to obtain an improved polarization during long cycling experiments compared to Cell 4. This can be attributed to the cohesive effect provided by styrene or polynorbornene, and therefore, confirms the positive and dispersive effect linked to the use of polynorbornene. Its complementarity with a more elastic polymer therefore ensures cohesion in cycling while allowing breathability of the system.
• Figure 13 shows a plot of discharge capacity and coulombic efficiency versus cycle number, and in (B) a plot of average charge and discharge potential versus cycle number for Cells 6 ( ⁇ ), 7 (A), 8 ( ⁇ ), 9 ( ⁇ ) and 10 ( ⁇ ).
• Figure 14 shows a graph of the average potential on charge and on discharge as a function of the number of cycles related to Figure 13 for Cells 6 ( ⁇ ), 7 (A), 8 ( ), 9 (T) and 10 ( ⁇ ).
• the retention of cycling capacity at C/3 and 30°C is little impacted by the change in formulation insofar as there is a polymer which can provide a cohesive effect (styrene or polynorbornene).
• a weaker polarization can be observed for the positive electrode film comprising a mixture of polybutadiene and polynorbornene (60:40 by weight) (Film 9) as binder, and this, especially in filler. This can be attributed to the dispersive effect of polynorbornene by the -COOH groups and by the carbon bridge it possesses, coupled with the repulsive and tt-p interactions of the carbons modified by polar groups and the coating of the sulfide particles by organic species with double or triple bonds.
• the cohesive character provided by the increase in the rate of polynorbornene vs polybutadiene makes it possible to ensure cycling stability while maintaining the particles and the contact between these particles, while polybutadiene makes it possible to absorb the variations in volume of the active material by cycling.

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