Electrode binders comprising a blend of a polybutadiene-based polymer and a polynorbornene-based polymer, electrodes comprising same and use thereof in electrochemistry

Abstract

The present invention relates to binder compositions and binders comprising a blend comprising a polybutadiene-based polymer and a polynorbornene-based polymer comprising norbornene-based monomer units derived from the polymerisation of an optionally substituted norbornene-based monomer for use in electrochemical applications, in particular in electrochemical storage cells such as batteries referred to as all-solid-state batteries. The invention also relates to electrode materials comprising said binder or said binder composition and the use thereof in electrochemical cells, for example in electrochemical storage cells, in particular in batteries referred to as all-solid-state batteries.

Description

[0001] ELECTRODE BINDERS COMPRISING A BLEND OF A POLYBUTADIENE-BASED POLYMER AND A POLYNORBORNENE-BASED POLYMER, ELECTRODES COMPRISING THEM AND THEIR USE

[0002] IN ELECTROCHEMISTRY RELATED APPLICATION

[0003] This application claims priority under applicable law from Canadian Provisional Patent Application No. 3,120,992 filed on June 3, 2021, the contents of which are incorporated herein by reference in their entirety and for all purposes.

[0004] TECHNICAL FIELD The present 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, electrode materials comprising them, their production methods and their use in electrochemical cells, in particular in so-called all-solid-state batteries. STATE OF THE ART

[0005] The development of polymer and / or ceramic-based solid electrolytes has made it possible to design all-solid-state electrochemical systems that are substantially safer, lighter, more flexible, and more efficient than their counterparts based on the use of liquid electrolytes. 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 an electronically conductive material. All of these could form a monolithic assembly.

[0006] One of the key elements of an all-solid-state electrochemical system is the dispersion of each of its constituents. Indeed, solid elements can tend to agglomerate during the mixing step with the binder, thus making the electrode material inhomogeneous. Among the strategies used to solve this problem, we find the encapsulation of the particles of the different constituents of the system with coating materials allowing a better dispersion of these. These dispersion problems can also be significantly reduced through the use of binders, additives or dispersion media leading to a better dispersion of the particles.

[0007] Norbornene-based polymers have been described as additives in PCT patent application WO2020 / 061710 (Daigle et al.), which are added to a polymer binder. Polynorbornenes are added, for example, to suppress or reduce side reactions such as the formation of lithium fluoride (LiF) and hydrofluoric acid (HF) resulting from the degradation of carbon-fluorine (CF) bonds. Korean Patent Publication No. KR 10-2193945 and PCT Patent Application Publication No. WO2019 / 004714 disclose a method for manufacturing a solid electrolyte film comprising a sulfide-based solid electrolyte and a composite electrode film for improving the dispersion, density, and ionic conductivity properties between the solid electrolyte particles and between the solid electrolyte particles and the active material particles by crystallization from an amorphous to a crystalline state.To do this, a norbornene-based copolymer is used, namely poly(ethylene-co-propylene-co-5-methylene-2-norbornene (PEPMNB).

[0008] However, there is still a need for the development of new materials for use in all-solid-state electrochemical systems with improved properties.

[0009] SUMMARY

[0010] In one aspect, the present technology relates to 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:

[0011] Formula I in which,

[0012] R 1 and R 2are independently and at each occurrence selected from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom and a chlorine atom. In one embodiment, the polynorbornene-based polymer is a polymer of

[0013] Formula II:

[0014] Formula II in which,

[0015] R 1 and R 2 are as defined herein, and n is a natural integer chosen such that the mass average molecular weight of the polymer of Formula II is between about 10,000 g / mol and about 100,000 g / mol, upper and lower bounds inclusive.

[0016] In another embodiment, 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 about 20,000 g / mol and about 65,000 g / mol, or between about 25,000 g / mol and about 55,000 g / mol, or between about 25,000 g / mol and about 50,000 g / mol, inclusive.

[0017] In another embodiment, 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 and R group 2 is a hydrogen atom. In another example, R 1 and R 2 are both -COOH groups.

[0018] In another embodiment, the polybutadiene-based polymer is polybutadiene. In another embodiment, the polybutadiene-based polymer is selected from epoxidized polybutadienes. In one example, the epoxidized polybutadiene comprises repeating units of Formulas III, IV, and V: and two terminal hydroxyl groups.

[0019] According to another example, epoxidized polybutadiene has Formula VI: wherein, m is a natural integer selected 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, upper and lower bounds inclusive; and the epoxide equivalent weight is between about 100 g / mol and about 600 g / mol, upper and lower bounds inclusive.

[0020] In another example, epoxidized polybutadiene is a Poly bd resin MC600E having a weight average molecular weight of about 1300 g / mol and an epoxy equivalent weight of about 400 g / mol to about 500 g / mol, both upper and lower bounds inclusive. In another example, the epoxidized polybutadiene is a Poly bd resin MC 605E having a weight average molecular weight of about 1300 g / mol and an epoxide equivalent weight of between about 260 g / mol and about 330 g / mol, upper and lower bounds inclusive.

[0021] In another embodiment, the weight ratio of polybutadiene-based polymer to polynorbornene-based polymer is in the range of about 6:1 to about 2:3, inclusive. For example, 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 about 4:1 to about 2:3, or about 6:1 to about 1:1, or about 5.5:1 to about 1:1, or about 5:1 to about 1:1, or about 4.5:1 to about 1:1, or about 4:1 to about 1:1, inclusive. According to a variant of interest, the weight ratio is in the range from about 4:1 to about 1:1, upper and lower limits included.

[0022] In another aspect, the present technology relates to a binder comprising a binder composition as defined herein. In one example, the binder is used in an electrode material.

[0023] In another aspect, the present technology relates to an electrode material comprising an electrochemically active material and a binder as defined herein.

[0024] In one embodiment, the electrochemically active material is selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium, and a combination of at least two thereof. For example, the metal of the electrochemically active material is selected 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 thereof. In one example, the electrochemically active material further comprises an alkali or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K), and magnesium (Mg).

[0025] In one embodiment, the electrochemically active material is selected 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, a metal fluoride, a metal sulfide, a metal oxysulfide, a carbon, silicon (Si), a silicon-carbon (Si-C) composite, a silicon oxide (SiO x ), a silicon oxide-carbon composite (SiO x -C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnO x ), a tin oxide-carbon composite (SnO x -C), and a combination of at least two thereof. In another embodiment, the electrochemically active material further comprises a doping element.

[0026] In another embodiment, the electrochemically active material is in the form of particles. For example, the electrochemically active material particles further comprise a coating material. In one example, the coating material is selected from LhSiOs, LUTisOia, LiTaOs, UAIO2, LhO-ZrOa, LiNbOs, other similar materials, and a combination of at least two thereof. In another example, the coating material is an electronically conductive material.

[0027] In another embodiment, the electrode material further comprises an electronically conductive material. For example, the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and a combination of at least two thereof. According to an example of interest, the surface of said electronically conductive material is grafted with at least one aryl group of Formula VII:

[0028] Formula VII in which,

[0029] FG is a hydrophilic functional group; and n is a natural integer in the range 1 to 5, preferably n is in the range 1 to 3, preferably n is 1 or 2, or more preferably n is 1.

[0030] In one example, the hydrophilic functional group is a carboxylic acid or sulfonic acid functional group. In another example, the aryl moiety of Formula VII is p-benzoic acid or p-benzenesulfonic acid. In another embodiment, the electrode material further comprises an additive. For example, the additive is selected from ionically conductive materials, inorganic particles, glass or glass-ceramic particles, ceramic particles, nanoceramics, salts, and a combination of two or more thereof. In one example, the additive comprises fluoride-, phosphide-, sulfide-, oxysulfide-, or oxide-based ceramic, glass, or glass-ceramic particles.According to another example, the additive is selected from compounds of the LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides, in crystalline and / or amorphous form, and a combination of at least two of these. According to another example, the additive is selected from inorganic compounds of formulas MLZO (for example, M7La3Zr20i2, M. (7-a) La3Zr2Al b Oi2, M (7. a)La3Zr2GabOi2, M (7 -a)La3Zr (2 -b)TabOi2, and M (7 -a)La3Zr (2 -b)NbbOi2); MLTaO (e.g., M7La3Ta20i2, M5La3Ta20i2, and M6LasTa1.5Y0.5O12); MLSnO (e.g., M7La3Sn20i2); MAGP (e.g. Mi +a Al a Ge 2-a (P04)3); MATP (e.g. Mi +a Al a You 2-a (P04) 3, ); MLTiO (e.g., M 3a There (2 / 3-a) Ti03); MZP (e.g., M a Zr b (P04) c ); MCZP (e.g., M aCabZr c (P04)d); MGPS (par example, M a GebPcSd tel que MioGeP2S-i2); MGPSO (see example, M a Ge b P c S d OR e ); MSiPS (for example, M a Yes b P c S d tel que M 10 S1P2S 12 ); MSiPSO (for example, M a Yes b P c S d OR e ); MSnPS (for example, M a Sn b P c S d tel que MioSnP2S-i2); MSnPSO (see example, M a Sn b P c S d OR e ); MPS (par exemple, M a P b S c tel que M7P3S 11 ); MPSO (par exemple, M a P b S c OR d ); MZPS (for example, M a Zn b P c S d ); MZPSO (for example, M a Zn b P c S d OR e); xlVbS-yPaSs; xlVbS-yPaSs-zMX; xlVhS-yPaSs-zPaOs; xlVbS- yP2S5-zP205-wMX; xlVbS-ylVbO-zPaSs; xlV S-ylV O-zPaSs-wMX; xlVhS-ylVhO-zPaSs- WP2O5; xM2S-yM20-zP2S5-wP205-vMX; xlVhS-ySiSa; MPSX (for example, M a P b S c X d such as M7P3S 11 X, M7P2S8X, et M6PS5X); MPSOX (for example, M a P b S c Oh d X e ); MGPSX (for example, M a Ge b P c S d X e ); MGPSOX (for example, M a Ge b P c S d Oh e X f ); MSiPSX (for example, M a Yes b P c S d X e ); MSiPSOX (for example, M a Yes b P c S d Oh e X f ); MSnPSX (for example, M a Sn b P c S d X e ); MSnPSOX (for example, M a Sn b P c S d Oh e Xf ); MZPSX (e.g., MaZn b PcSdXe); MZPSOX (e.g., M a ZnbP c SdO e Xf); M3OX; M2HOX; M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which:

[0031] 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 thereof; a, b, c, d, e, and f are nonzero numbers and are, independently in each formula, selected to achieve electroneutrality; and v, w, x, y, and z are nonzero numbers and are, independently in each formula, selected to achieve a stable compound.

[0032] According to a variant of interest, the additive is chosen from inorganic compounds of the argyrodite type of formula LÎ6PS5X in which X is Cl, Br, I or a combination of at least two of these. For example, the additive is LÎ6PS5CI.

[0033] In another aspect, the present technology relates to an electrode comprising the electrode material as defined herein on a current collector. In another aspect, the present technology relates to a self-supporting electrode comprising the electrode material as defined herein.

[0034] In another aspect, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive electrode or the negative electrode is as defined herein or comprises an electrode material as defined herein.

[0035] In another embodiment, the electrolyte is a liquid electrolyte comprising a salt in a solvent.

[0036] In another embodiment, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

[0037] In another embodiment, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

[0038] In another embodiment, the electrolyte is a polymer-ceramic hybrid solid electrolyte. In another embodiment, the electrolyte comprises an inorganic solid electrolyte material. In one example, the inorganic solid electrolyte material comprises fluoride, phosphide, sulfide, oxysulfide, or oxide-based ceramic, glass, or glass-ceramic particles. In another example, the inorganic solid electrolyte material is selected from LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides, in crystalline and / or amorphous form, and a combination of at least two thereof. According to another example, the inorganic solid electrolyte material is selected from inorganic compounds of formulas MLZO (e.g., M7La3Zr20i2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a) La3Zr(2-b)TabOi2, and M(7-a >La3Zr(2- b)Nb b Oi2); MLTaO (e.g., M7La3Ta2Oi2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (e.g., M7La3Sn20i2); MAGP (e.g., Mi +a Al a Ge2- a (P04)3); MATP (e.g., Mi +a Al a Ti2- a (P04)3,); MLTiO (e.g., M3 a The(2 / 3- a >Ti03); MZP (e.g., M a Zrb(P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., MgGe b P c S d such that Mi0GeP2Si2); MGPSO (e.g., M a Here b P c S d OH e ); MSiPS (e.g., M a If b P c S d such that M 10 S1P2S 12 ); MSiPSO (e.g., M a If b P c S d OH e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., Ma Sn b P c S d O e ); MPS (e.g., M a P b S c such as M7P3S 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 O e ); xM2S-yP2S5; xM2S-yP2S5- zMX; xM2S-yP2S5-zP205; xM2S-yP2S5-zP205-wMX; xM2S-yM20-zP2S5; xM2S-yM20- ZP2S5-WMX; xM2S-yM20-zP2S5-wP205; xM2S-yM20-zP2S5-wP205-vMX; xM2S-ySiS2; MPSX (e.g., M a P b S c X d such as M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (e.g., M a P b S c O d X e ); MGPSX (e.g., M a Ge b P c S d X e ); MGPSOX (e.g., MgGe b P c S d O e X f); MSiPSX (e.g., M a If b P c S d X e ); MSiPSOX (e.g., M a If b P c S d O e X f ); MSnPSX (e.g., M a Sn b P c S d X e ); MSnPSOX (e.g., MgSn b P c S d O e X f ); MZPSX (e.g., M a Zn b P c S d X e ); MZPSOX (e.g., M a Zn b P c S d O e X f ); M3OX; M2HOX; M3P04; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which:

[0039] 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;

[0040] X is selected from F, Cl, Br, I or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers 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 obtain a stable compound. According to a variant of interest, the inorganic solid electrolyte material is selected from inorganic argyrodite compounds of formula LÎ6PS5X in which X is Cl, Br, I or a combination of at least two thereof. For example, the inorganic solid electrolyte material is LÎ6PS5CI. According to another aspect, the present technology relates to an electrochemical accumulator comprising at least one electrochemical cell as defined herein.

[0041] In another embodiment, the electrochemical accumulator is a battery selected from 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-state battery.

[0042] BRIEF DESCRIPTION OF THE FIGURES

[0043] Figure 1 shows in (A) an SEM image of Film 1, 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. The scale bars represent 300 pm and 100 pm, respectively.

[0044] 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. The scale bars represent 100 pm. 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. The scale bars represent 100 pm.

[0045] 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. The scale bars represent 100 pm.

[0046] 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. The scale bars represent 100 pm. Figure 6 shows in (A) an SEM image of Film 7 allowing the observation of the different layers of the film, and in (B) a top view SEM image of this same film, as described in Example 4. The scale bars represent 100 pm.

[0047] Figure 7 shows in (A) an SEM image of Film 8 allowing observation of the different layers of the film, and in (B) an SEM image seen from above of this same film, as described in Example 4. The scale bars represent 100 pm.

[0048] Figure 8 shows in (A) an SEM image of Film 9 allowing observation of the different layers of the film, and in (B) a top view SEM image of this same film, as described in Example 4. The scale bars represent 100 pm. Figure 9 shows a graph of the discharge capacity (mAh / g) and the coulombic efficiency (%) as a function of the number of cycles for Cell 1 ( ■ ) and Cell 2 (A), as described in Example 5(b).

[0049] Figure 10 shows a graph of the average charge and discharge potential (V) versus the number of cycles for Cell 1 ( ■ ) and Cell 2 (A), as described in Example 5(b).

[0050] 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).

[0051] Figure 12 shows a graph of the average charge and discharge potential (V) versus the number of cycles for Cell 3 ( ■ ), Cell 4 (·) and Cell 5 (A), as described in Example 5(b).

[0052] Figure 13 shows in (A) a plot of discharge capacity and coulombic efficiency (%) as a function of cycle number 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 the average charging and discharging potential (V) versus the number of cycles for Cell 6 ( ■ ), Cell 7 (A), Cell 8 (·), Cell 9 (T) and Cell 10 as described in Example 5(b).

[0053] DETAILED DESCRIPTION All technical and scientific terms and expressions used herein have the same definitions as those generally understood by those skilled in the art of the present technology. Definitions of certain terms and expressions used are nevertheless provided below.

[0054] When the term "about" is used here, it means approximately, in the region of, or around. For example, when the term "about" is used in connection with a numerical value, it modifies it above and below by a variation of 10% from its nominal value. This term may also take into account, for example, the experimental error of a measuring device or rounding.

[0055] Where a range of values ​​is referred to in this application, the lower and upper bounds of the range are, unless otherwise indicated, always included in the definition. Where a range of values ​​is referred to in this application, then all intermediate ranges and sub-ranges, as well as individual values ​​included in ranges of values, are included in the definition.

[0056] When the article "a" is used to introduce an element in the present application, it does not have the meaning of "a single one", but rather of "one or more". Of course, where the description states that a particular step, component, element or feature "may" or "could" be included, that particular step, component, element or feature is not required to be included in every embodiment.

[0057] For clarity, the term "monomer units derived from" and equivalent terms, as used herein, refer to repeating polymer units obtained from the polymerization of a polymerizable monomer.

[0058] The term "aryl" as used herein refers to substituted or unsubstituted aromatic rings, wherein the contributing atoms may form one ring or a plurality of fused rings. Representative aryl groups include groups having from 6 to 14 ring members. For example, aryl may include phenyl, naphthyl, etc. The aromatic ring may be substituted at one or more positions of the ring with, for example, a carboxyl (-COOH) or sulfonic acid (-SO3H) group, an amine group, and the like. The term "hydrophilic functional group," as used herein, refers to functional groups attracted to water molecules. Hydrophilic functional groups may generally be charged and / or capable of forming hydrogen bonds.Non-limiting examples of hydrophilic functional groups include hydroxyl, carboxyl, sulfonic acid, phosphonic acid, amine, amide and other similar groups. The term further encompasses salts of these groups, where applicable.

[0059] The term "freestanding electrode" as used herein refers to an electrode without a metallic current collector. The chemical structures described herein 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 if they are not explicitly drawn.

[0060] The present technology relates to an electrode binder comprising a polymer blend, more specifically to an electrode binder comprising a polymer blend for use in so-called all-solid-state electrochemical systems.

[0061] More particularly, the present technology relates to an electrode binder comprising a blend 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:

[0062] Formula I in which,

[0063] R 1 and R 2 are independently and at each occurrence chosen from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom and a chlorine atom. According to one example, at least one of R 1 or R 2is chosen from -COOH, -SO3H -OH, F, and Cl, which means that at least one of R 1 or R 2 is different from a hydrogen atom.

[0064] According to another example, R 1 is a -COOH and R group 2 is a hydrogen atom.

[0065] According to another example, 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 by a carboxylic acid. According to a variant of interest, R 1 is a -COOH and R group 2 is a hydrogen atom. According to another variant of interest, R 1 and R 2 are both -COOH groups.

[0066] 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:

[0067] Formula II in which,

[0068] R 1 and R 2 are as defined above, and n is a natural integer chosen such that the mass average molecular weight of the polymer of Formula II is between about 10,000 g / mol and about 100,000 g / mol as determined by gel permeation chromatography (GPC), upper and lower bounds inclusive. In another example, 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, or between about 20,000 g / mol and about 65,000 g / mol, or between about 25,000 g / mol and about 55,000 g / mol, or between about 25,000 g / mol and about 50,000 g / mol as determined by GPC, upper and lower bounds inclusive.

[0069] According to a variant of interest, R 1 and R 2are -COOH groups. According to another example, the polymer based on polynorbornene is of Formula ll(a): in which,

[0070] R 2 and n are as defined previously.

[0071] According to another example, the polymer based on polynorbornene is of Formula 11(b):

[0072] Formula 11(b) in which, n is as defined previously.

[0073] According to another example, the polymer based on polynorbornene of Formulas II, 11(a) or 11(b) is a homopolymer.

[0074] According to another example, the polymerization of a norbornene-based monomer of Formula I can be carried out by all known and compatible polymerization methods. According to an alternative of interest, the polymerization of the compound of Formula I can be carried out by the synthetic method described by Commarieu, B. et al. (Commarieu, Basile, et al. "Ultrahigh T gEpoxy Thermosets Based on Insertion Polynorbornenes", Macromolecules, 49.3 (2016): 920-925). For example, the polymerization of the compound of Formula I can also be carried out by an addition polymerization process. For example, polynorbornene-based polymers produced by an addition polymerization process can be substantially stable under severe conditions (e.g., acidic and basic conditions). Addition polymerization of polynorbornene-based polymers can be carried out using inexpensive norbornene-based monomers. The glass transition temperature (T v ) obtained with the polynorbornene-based polymers produced by this polymerization route may be equal to or greater than about 300°C, e.g., as high as 350°C.

[0075] In another example, the polybutadiene-based polymer may be characterized by substantially higher elasticity or flexibility and / or a glass transition temperature (T v ) substantially lower than those of the polymer based on polynorbornene of Formulas II, II(a) or II(b).

[0076] In another example, the polybutadiene-based polymer may be polybutadiene. Alternatively, the polybutadiene-based polymer may be functionalized polybutadiene or a polybutadiene-derived polymer. For example, compared to non-functionalized polybutadiene, the functionalized polybutadiene or the polybutadiene-derived polymer may be characterized by substantially higher elasticity or flexibility, and / or by a glass transition temperature (T v) substantially lower and / or may improve the mechanical or cohesive properties of the electrode binder. According to another example, the polybutadiene-based polymer is selected from epoxidized polybutadienes, for example, epoxidized polybutadienes having reactive end groups. For example, the reactive end groups may be hydroxyl groups. The epoxidized polybutadiene may comprise repeating units of Formulas III, IV and V:

[0077] Formula III Formula IV Formula V and two hydroxyl end groups. In another example, the mass average molecular weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V may be between about 1000 g / mol and about 1500 g / mol as determined by GC, inclusive of upper and lower limits. In another example, 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 GC, inclusive of upper and lower limits. The epoxide equivalent weight corresponds to the mass of resin which contains 1 mole of epoxide functional groups. In a variant of interest, the epoxidized polybutadiene is of Formula VI: wherein, m is a natural integer selected such that the mass average molecular weight of the epoxidized polybutadiene of Formula VI is between about 1,000 g / mol and about 1,500 g / mol as determined by GPC, inclusive of the upper and lower limits; and the epoxide equivalent weight is between about 100 g / mol and about 600 g / mol as determined by GPC, inclusive of the upper and lower limits. In another example, the mass average molecular weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V or the epoxidized polybutadiene of Formula VI is between about 1050 g / mol and about 1450 g / mol, or between about 1100 g / mol and about 1400 g / mol, or between about 1150 g / mol and about 1350 g / mol, or between about 1200 g / mol and about 1350 g / mol, or between about 1250 g / mol and about 1350 g / mol as determined by GPC, upper and lower bounds inclusive.According to an alternative embodiment of interest, the mass average molecular weight of 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.

[0078] In another example, the epoxide equivalent weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V or the epoxidized polybutadiene of Formula VI is between about 150 g / mol and about 550 g / mol, or between about 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 GC, inclusive of upper and lower limits. In a variant of interest, the epoxide equivalent weight of the epoxidized polybutadiene comprising repeating units of Formulas III, IV and V or the epoxidized polybutadiene of Formula VI is between about 400 g / mol and about 500 g / mol, or between about 260 g / mol and about 330 g / mol as determined by GC, inclusive of upper and lower limits.

[0079] For example, epoxidized polybutadiene of Formula VI is a commercial epoxidized polybutadiene resin having hydroxyl end groups of the Poly bd type MC 600E or 605E marketed by Cray Valley. The physicochemical properties of these resins are presented in Table 1.

[0080] Table 1. Physicochemical properties of Poly bd 600E or 605E type resins

[0081] It is understood that the electrode binder comprises a polymer blend comprising at least one first polymer and at least one 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).

[0082] In another example, the ratio of "first polymer:second polymer" is in the range of about 6:1 to about 2:3, inclusive. For example, the ratio of "first polymer:second polymer" 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 about 4:1 to about 2:3, or about 6:1 to about 1:1, or about 5.5:1 to about 1:1, or about 5:1 to about 1:1, or about 4.5:1 to about 1:1, or about 4:1 to about 1:1, inclusive. According to a variant of interest, the ratio “first polymer: second polymer” is in the range from about 4:1 to about 1:1, upper and lower limits inclusive.

[0083] In another example, the polymer blend of said electrode binder may be solubilized in at least one solvent. For example, the solvent may be selected for its ability to solubilize and be efficiently mixed with the polymer blend. For example, the solvent may be an organic solvent, e.g., a polar aprotic solvent. For example, the solvent may 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 thereof.According to a variant of interest, 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, a mixture comprising m-xylene and THF, a mixture comprising o-xylene and THF, a mixture comprising p-xylene and DEC, a mixture comprising m-xylene and DEC, a mixture comprising o-xylene and DEC, or a mixture comprising toluene and methoxybenzene. However, this solvent is preferably removed from the electrode in which the binder is found before its assembly with other elements of an electrochemical cell.

[0084] The present technology also relates to the use of the electrode binder as defined herein in an electrode material. Indeed, an electrode material comprising an electrode material including an electrochemically active material and an electrode binder as defined herein is also contemplated.

[0085] In one example, the electrode material as defined herein further includes an electronically conductive material. Non-limiting examples of electronically conductive material include a carbon source such as carbon black (e.g., Ketjen carbon MC and Super P carbon MC ), acetylene black (e.g., Shawinigan carbon and Denka carbon black MC ), graphite, graphene, carbon fibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs), and a combination of two or more of these.

[0086] In another example, the electronically conductive material, if present in the electrode material, may be a modified electronically conductive material such as those described in PCT patent application published under number WO2019 / 218067 (Delaporte et al.). For example, the modified electronically conductive material may be grafted with at least one aryl group of Formula VII:

[0087] Formula VII in which,

[0088] FG is a hydrophilic functional group; and n is a natural integer 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.

[0089] Examples of hydrophilic functional groups include hydroxyl, carboxyl, sulfonic acid, phosphonic acid, amine, amide, and other similar groups. For example, the hydrophilic functional group is a carboxyl or sulfonic acid functional group. Preferred examples of an aryl group of Formula VII include p-benzoic acid and p-benzenesulfonic acid.

[0090] According to one variant of interest, the electronically conductive material is carbon black optionally grafted with at least one aryl group of Formula VII. According to another variant of interest, the electronically conductive material may be a mixture comprising at least one modified electronically conductive material. For example, a mixture of carbon black grafted with at least one aryl group of Formula VII and carbon fibers (e.g., gas-formed carbon fibers (VGCFs)), carbon nanofibers, carbon nanotubes (CNTs) or a combination of at least two of these.According to another example, said electrode material is a positive electrode material and the electrochemically active material is selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide (e.g., a metal fluoride), sulfur, selenium, and a combination of at least two thereof. According to another example, the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and combinations thereof, 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).

[0091] Non-limiting examples of electrochemically active materials include lithium metal phosphates, complex oxides, such as LiM'PC (where M' is Fe, Ni, Mn, Co, or a combination thereof), UV3O8, V2O5, LiM^C, LiM”02 (where M” is Mn, Co, Ni, or a combination thereof), Li(NiM'”)02 (where M'” is Mn, Co, Al, Fe, Cr, Ti, or Zr, or a combination thereof) and combinations thereof, where compatible.

[0092] According to a variant of interest, the electrochemically active material is an oxide or a phosphate such as those described above.

[0093] For example, the electrochemically active material is a lithium manganese oxide, wherein the manganese may be partially substituted by a second transition metal, such as a lithium nickel manganese cobalt (NMC) oxide. Alternatively, the electrochemically active material is lithium iron phosphate. Alternatively, the electrochemically active material is a manganese-containing lithium metal phosphate such as those described above, e.g., the manganese-containing lithium metal phosphate is a lithium iron manganese phosphate (LiMni- x Fe x P04, where x is between 0.2 and 0.5).

[0094] According to another example, said electrode material is a negative electrode material and the electrochemically active material is selected from a non-alkali and non-alkaline earth metal (e.g., indium (In), germanium (Ge) and bismuth (Bi)), an intermetallic compound (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiThiPO^), a metal halide (e.g., a metal fluoride), a metal sulfide, a metal oxysulfide, a carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite and amorphous 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-carbon composite (Sn-C), a tin oxide (SnO x), a tin oxide-carbon composite (SnO x -C), and combinations thereof, when compatible. For example, the metal oxide may be chosen from compounds of formulas 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 c:b ratio is in the range from 2 to 3) (e.g., M0O3, M0O2, M0S2, V2O5, and TiNb207), spinel oxides (e.g., N1C02O4, ZhOq2q4, MnCo204, CUC02O4, and CoFe2O4) and LiM””O (where M'”” is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination of two or more thereof) (e.g., a lithium titanate (such as Li4Ti5Oi2) or a lithium molybdenum oxide (such as U2M04O 13 )).

[0095] According to another example, the electrochemically active material may optionally be doped with other elements included in smaller amounts, for example to modulate or optimize its electrochemical properties. The electrochemically active material may be doped by partial substitution of the metal with other ions. For example, the electrochemically active material may 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 (e.g., Mg, Al, or Sb).

[0096] According to another example, the electrochemically active material may be in the form of particles (e.g., microparticles and / or nanoparticles) which may be freshly formed or commercially sourced. For example, the electrochemically active material may be in the form of particles coated with a layer of coating material in a core-shell configuration. The coating material may be an electronically conductive material, for example, a conductive carbon coating. The conductive carbon layer may also be optionally grafted with at least one aryl group of Formula VII. Alternatively, the coating material may substantially reduce interfacial reactions at the interface between the electrochemically active material and an electrolyte, for example, a solid electrolyte, and in particular, a sulfide-based ceramic-type solid electrolyte (e.g., based on LÎ6PS5CI).For example, the coating material may be selected from LhSiOs, LUTisO·^, LiTaOs, UAIO2, LÎ20-Zr02, LiNb03, combinations thereof, when compatible, and other similar materials. According to an alternative embodiment, the coating material comprises LiNbOs.

[0097] According to another example, the electrode material as defined herein further includes an additive. For example, the additive is selected from ionic conductive materials, inorganic particles, glass or glass-ceramic particles, ceramic particles, including nanoceramics (e.g., AI2O3, T1O2, S1O2 and other similar compounds), salts (e.g., lithium salts) and a combination of at least two thereof. For example, the additive may be an ionic conductor selected from compounds of the LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, sulfur halides, phosphates, thio-phosphates, crystalline and / or amorphous deformed, and a combination of at least two thereof.

[0098] According to an alternative embodiment of interest, the additive, if present in the electrode material, may be ceramic, glass, or glass-ceramic particles of crystalline and / or amorphous form. For example, the ceramic, glass, or glass-ceramic particles may be based on fluoride, phosphide, sulfide, oxysulfide, oxide, or a combination of two or more thereof. Non-limiting examples of ceramic, glass, or glass-ceramic particles include inorganic compounds of formulas MLZO (e.g., M7La3Zr20i2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a) La3Zr (2-b) Your b Oi2, and M ( 7- a) La3Zr ( 2- b) Nb b Oi2); MLTaO (e.g., M7La3Ta2Oi2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (e.g., M7La3Sn20i2); MAGP (e.g. Mi +a Al a Ge2- a (P04)3); MATP (e.g. Mi +a Al a TÎ2-a (P04)3); MLTiO (e.g., M 3a The (2 / 3-a >Ti03); MZP (e.g., M a Zr b (P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., M a GebP c Sd such as MioGeP2Si2); MGPSO (e.g., M a Here b P c S d OH e ); MSiPS (e.g., M a If b P c S d such that M 10 S1P2S 12 ); MSiPSO (e.g., M a If b P c S d OH e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., M a Sn b P c S d OH e ); MPS (e.g., M a P b S c such as M7P3S 11 ); MPSO (e.g., M a P b S c OH d ); MZPS (e.g., M a Zn b Pc S d ); MZPSO (par exemple, MaZnbPcSdOe); xM2S-yP2S5; xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; xM2S-yP2S5-zP205- wMX; xM2S-yM20-zP2S5; xM2S-yM20-zP2S5-wMX; xM2S-yM20-zP2S5-wP205; XM2S- yM20-zP2S5-wP205-vMX; xM2S-ySiS2; MPSX (par exemple, M a P b S c X d tel que M7P3S 11 X, M7P2S8X, et M6PS5X); MPSOX (par exemple, M a P b S c O d X e ); MGPSX (par exemple, M a Ge b P c S d X e ); MGPSOX (par exemple, M a Ge b P c S d O e X f ); MSiPSX (par exemple, MaSi b PcS d Xe); MSiPSOX (par exemple, M a Si b PcS d O e X f ); MSnPSX (par exemple, MaSri b PcS d Xe); MSnPSOX (par exemple, M a Sn b PcS d O e X f); MZPSX (e.g., MaZribPcSdXe); MZPSOX (e.g., M a ZnbPcSdO e Xf); M3OX; M2HOX; M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which:

[0099] 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;

[0100] X is selected from F, Cl, Br, I or a combination of at least two thereof; a, b, c, d, e and f are non-zero numbers 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 obtain a stable compound.

[0101] For example, M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and a combination of at least two thereof. According to a variant of interest, 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 thereof. According to a variant of interest, M comprises Na, K, Mg or a combination of at least two thereof.

[0102] For example, the additive, if present in the electrode material, may be sulfide-based ceramic particles, for example, argyrodite-type ceramic particles of formula LÎ6PS5X (where X is Cl, Br, I or a combination of at least two of these). In a variant of interest, the additive is argyrodite LÎ6PS5CI.

[0103] For example, the method of preparing the electrode material as defined herein further includes the use of a solvent, for example, an organic solvent. For example, the solvent may provide an optimum viscosity for coating the electrode material, i.e., about 10,000 cP, and may be substantially removed in a post-coating drying step. For example, the solvent may be THF or methoxybenzene (or anisole).

[0104] The present technology also relates to an electrode comprising an electrode material as defined herein. In one example, the electrode may be on a current collector (e.g., aluminum or copper foil). Alternatively, the electrode may be self-supporting.

[0105] 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.

[0106] According to a variant of interest, the negative electrode is as defined herein. For example, the electrochemically active material of the negative electrode may be chosen for its electrochemical compatibility with the various elements of the electrochemical cell as defined herein. For example, the electrochemically active material of the negative electrode material may have a substantially lower oxidation-reduction potential than that of the electrochemically active material of the positive electrode.

[0107] According to another variant of interest, the positive electrode is as defined herein and the negative electrode includes an electrochemically active material selected from all known compatible electrochemically active materials. For example, the electrochemically active material of the negative electrode may be chosen for its electrochemical compatibility with the various elements of the electrochemical cell as defined herein. Non-limiting examples of negative electrode electrochemically active 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., indium (In), germanium (Ge) and bismuth (Bi)), and intermetallic alloys or compounds (e.g., SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2).For example, the electrochemically active material of the negative electrode may be in the form of a film having a thickness in the range of about 5 μm to about 500 μm and preferably in the range of about 10 μm to about 100 μm, upper and lower limits inclusive. According to an alternative embodiment of interest, the electrochemically active material of the negative electrode may comprise a film of metallic lithium or an alloy including metallic lithium.

[0108] According to another example, the positive electrode may be prelithiated and the negative electrode may be initially (i.e., before cycling of the electrochemical cell) substantially or completely free of lithium. The negative electrode may be lithiated in situ during cycling of said electrochemical cell, in particular during the first charge. According to one example, metallic lithium may be deposited in situ on the current collector (e.g., a copper current collector) during cycling of the electrochemical cell, in particular during the first charge. According to another example, an alloy including metallic lithium may be generated on the surface of a current collector (e.g., an aluminum current collector) during cycling of the electrochemical cell, in particular during the first charge. It is understood that the negative electrode may be generated in situ during cycling of the electrochemical cell, in particular during the first charge.

[0109] According to another variant of interest, the positive electrode and the negative electrode are both as defined herein.

[0110] In another example, the electrolyte may be chosen for its compatibility with the various elements of the electrochemical cell. Any type of compatible electrolyte is considered. In one example, the electrolyte is a liquid electrolyte comprising a salt in a solvent. In one alternative, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. In another alternative, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer. In another alternative, the electrolyte comprises an inorganic solid electrolyte material, for example, the electrolyte may be a ceramic-type solid electrolyte. In another alternative, the electrolyte is a polymer-ceramic hybrid solid electrolyte.

[0111] As another example, the salt, if present in the electrolyte, may be an ionic salt, such as a lithium salt. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPFe), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium 2-trifluoromethyl-4,5-dicyanoimidazolate (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 (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (UCIO4), lithium hexafluoroarsenate (LiAsFe), lithium trifluoromethanesulfonate (USO3CF3) (LiTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP),lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-0.0')borate Li[B(C602)2] (LiBBB), lithium difluoro(oxalato)borate (LiBF2(C204)) (LiFOB), a salt of formula LiBF204R, x (in which, R x = C2-C4alkyl), and a combination of at least two of these.

[0112] In another example, the solvent, if present in the electrolyte, may be a non-aqueous solvent. Non-limiting examples of 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 γ-butyrolactone (g-BL) and γ-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-dioxolane and dioxolane derivatives;and other solvents such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, phosphoric acid triesters, sulfolane, methylsulfolane, propylene carbonate derivatives and mixtures thereof.;

[0113] In another example, the electrolyte is a gel electrolyte or a gel polymer electrolyte. The gel polymer electrolyte may comprise, for example, a polymer precursor and a salt (e.g., a salt as defined above), a solvent (e.g., a solvent as defined above), and a polymerization and / or crosslinking initiator, if desired. Examples of gel electrolyte include, but are not limited to, gel electrolytes such as those described in PCT patent applications published under numbers WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0114] In another example, a gel electrolyte or a liquid electrolyte as defined above may also impregnate a separator such as a polymer separator. Examples of separators include, but are not limited to, polyethylene (PE), polypropylene (PP), cellulose, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), and polypropylene-polyethylene-polypropylene (PP / PE / PP) separators. For example, the separator is a commercial polymer separator such as Celgard. MC. In another example, the electrolyte is a solid polymer electrolyte. For example, the solid polymer electrolyte composition may be selected from any known solid polymer electrolyte composition and may be selected 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 polyethylene oxide (PEO), may be used, but several other compatible polymers are also known for the preparation of solid polymer electrolytes and are also contemplated. The polymer may be crosslinked.Examples of such polymers include branched polymers, e.g., star polymers or comb polymers such as those described in PCT patent application published under number WO2003 / 063287 (Zaghib et al.).

[0115] According to another example, the solid polymer electrolyte composition may include a block copolymer composed of at least one lithium ion solvation segment and optionally at least one crosslinkable segment. Preferably, the lithium ion solvation segment is selected from homo- or copolymers having repeating units of Formula VIII: (CH2-CH-0) x -

[0116] R

[0117] Formula VIII in which,

[0118] R is chosen from a hydrogen atom, and a C1-C10alkyl group or a -(CH2-O-R a R b );

[0119] R a is (CH2-CH2-0) y ;

[0120] R bis selected from a hydrogen atom and a C1-C10alkyl group; x is an integer selected from the range of 10 to 200,000; and y is an integer selected from the range of 0 to 10.

[0121] In another example, the crosslinkable segment of the copolymer is a polymer segment comprising at least one functional group that is multidimensionally crosslinkable by irradiation or heat treatment. In another example, the electrolyte comprises an ionically conductive inorganic solid electrolyte material and may comprise ceramic, glass, or glass-ceramic particles. For example, ceramic, glass, or glass-ceramic particles based on fluoride, phosphide, sulfide, oxysulfide, oxide, or a combination of at least two thereof. In a variant of interest, the electrolyte comprises ceramic, glass, or glass-ceramic particles as described above.

[0122] According to another example, the electrolyte is a polymer-ceramic hybrid solid electrolyte, and may, for example, comprise particles of inorganic material as defined herein, previously dispersed in a solid polymer electrolyte as defined above. Alternatively, 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.

[0123] In another example, the electrolyte may also optionally include additives such as ionically conductive materials, inorganic particles, glass or ceramic particles as defined above, and other additives of the same type. In another example, the additive may be a dicarbonyl compound such as those described in PCT patent application published under number WO2018 / 116529 (Asakawa et al.). For example, the additive may be poly(ethylene-alt-maleic anhydride) (PEMA). The additive may be selected from any known electrolyte additives and may be chosen for its compatibility with the various elements of the electrochemical cell. In one example, the additive may be substantially dispersed in the electrolyte. Alternatively, the additive may be present in a separate layer.

[0124] According to one example, the electrode binder comprising a polymer blend as defined herein can significantly improve the dispersion of the various constituents of the positive electrode material, in particular the solid constituents. For example, the electrode binder comprising a polymer blend as defined herein can substantially promote the dispersion of the electrochemically active material, the electronically conductive material and / or the ceramic-type solid electrolyte material. For example, the R groups 1 and / or R 2of the polynorbornene-based polymer of the polymer blend of said binder may be groups that can promote the dispersion of one of these materials. For example, carboxyl groups (-COOH) may be groups that can promote the dispersion of one of these materials. Without wishing to be bound by theory, for example, repulsive interactions linked to the polymer blend 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. For example, the repulsive interactions may be pp-type and / or polar interactions.

[0125] According to another example, the various constituents of the positive electrode material may be modified in order to substantially increase the repulsive interactions with the polymer mixture of said binder, and thus, to promote their dispersion. For example, the various constituents of the positive electrode may be modified by coating them with a coating material encouraging repulsive interactions, for example, pp-type and / or polar interactions. According to one example, at least one of the electrochemically active material, the electronically conductive material and the ceramic-type electrolyte material may be coated with a coating material encouraging repulsive interactions. For example, the coating material may comprise at least one branched or linear unsaturated aliphatic hydrocarbon having from 10 to 50 carbon atoms and having at least one carbon-carbon double or triple bond.For example, such a coating material may be a mixture comprising said unsaturated aliphatic hydrocarbon and an additional component. The additional component may be an alkane (e.g., an alkane having from 10 to 50 carbon atoms) or a mixture comprising an alkane (e.g., as defined herein) and a polar solvent (e.g., tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or a miscible combination of at least two thereof). According to an alternative embodiment of interest, the additional component is decane or a mixture comprising decane and tetrahydrofuran. A conductive material, such as a carbon, may also be modified by the grafting of groups, for example, as described in the PCT patent application published under number WO2019 / 218067. According to an example, the electrochemical performance of the positive electrode material is not substantially negatively affected by these modifications and their interactions.Ionic and electronic conduction phenomena can even be favored, as well as the electrochemical double layer presenting better stability.

[0126] The present technology also relates to a battery comprising at least one electrochemical cell as defined herein. For example, the battery may be a primary (cell) or secondary (accumulator) battery. According to one example, the battery is selected from the group consisting of a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, a magnesium-ion battery, a potassium battery and a potassium-ion battery. According to a variant of interest, the battery is a so-called all-solid-state battery.

[0127] EXAMPLES

[0128] The following examples are illustrative and should not be interpreted as further limiting the scope of the invention as contemplated. These examples will be better understood by referring to the accompanying Figures. Example 1 - Preparation of argyrodite-type ceramic particles of formula LiePSsCI a) Coating of LiePSsCI particles with a mixture of heptane and dibutyl ether (50:50 by volume)

[0129] The coating of LiePSsCI particles was carried out by a wet particle grinding process.

[0130] Coating of LiePSsCI particles was carried out during wet particle grinding to reduce particle size and using a PULVERISETTE planetary micromill. MC7. 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) grinding jar. A mixture comprising 13 mL of heptane and 13 mL of anhydrous dibutyl ether (50:50 by volume) along with 2 mm diameter grinding balls 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 dibutyl ether. The resulting particles were subsequently dried under vacuum at a temperature of about 80 °C. b) Coating of LkPSsCI particles with a mixture of decane and squalene (75:25 by volume) The coating of the LÎ6PS5CI particles was carried out by a process of particle grinding and wet mechanosynthesis.

[0131] Coating of Li6PS5CI particles was carried out using a PULVERISETTE planetary micromill MC 7. 4 g of Li6PS5CI 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) along with 2 mm diameter grinding balls were added to the jar. The Li6PS5CI particles and the mixture of decane and squalene were combined by grinding at a speed of about 300 rpm for about 7.5 hours to produce Li6PS5CI particles coated with the mixture of decane and squalene. The resulting particles were subsequently dried under vacuum at a temperature of about 80 °C. c) Coating of Li6PS5CI particles with mixture of decane and squalene (90:10 by volume)

[0132] The coating of the LÎ6PS5CI particles was carried out by a process of particle grinding and wet mechanosynthesis.

[0133] Coating of the LÎ6PS5CI particles was carried out using a PULVERISETTE planetary micromill MC 7. 4 g of LÎ6PS5CI particles were placed in an 80 ml zirconium oxide grinding jar. A mixture of decane and squalene (90:10 by volume) and 2 mm diameter grinding balls were added to the jar. The LÜ6PS5CI particles and the mixture of decane and squalene were combined by grinding at a speed of about 300 rpm for about 7.5 hours to produce LÜ6PS5CI particles coated with the mixture of decane and squalene. The particles thus obtained were subsequently dried under vacuum at a temperature of about 80 °C. Example 2 - Preparation of the modified electronically conductive material a) Grafting of the electronically conductive material particles with at least one aryl group of Formula VII

[0134] The following method for the production of electronically conductive material was applied to carbon black. 5 g of carbon black was dispersed in 200 ml of 0.5 M aqueous sulfuric acid (H2SO4) solution, and then 0.01 equivalent of aniline p-substituted with a hydrophilic substituent (-SO3H which was then lithiated in order to exchange hydrogen with lithium) was added to the mixture (i.e. 0.01 equivalent of aniline relative to carbon black). The mixture was then stirred vigorously until the amine was completely dissolved.

[0135] After addition of 0.03 equivalents of sodium nitrite (NaNO2) relative to carbon black (e.g., 3 equivalents of NaNO2 relative to aniline), the corresponding aryl diazonium ion was generated in situ and reacted with the carbon black. The resulting mixture was left to react overnight at room temperature.

[0136] After the reaction was completed, the mixture was vacuum filtered using a vacuum filtration assembly (Büchner type) and a nylon filter with a pore size of 0.22 μm. The modified carbon black powder thus obtained was then washed successively with deionized water until a neutral pH was reached, then with acetone. Finally, the modified carbon black powder was then dried under vacuum at 100°C for at least one day before use. b) Coating of the electronic conductive material particles with a mixture of decane and squalene (75:25 by volume)

[0137] The coating of the particles of electronically conductive material is carried out by a process of particle grinding and wet mechanosynthesis.

[0138] Coating of carbon black particles is carried out using a PULVERISETTE planetary micromill MC7. 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) and 2 mm diameter grinding balls 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 carbon black particles coated with the mixture of decane and squalene. The particles thus obtained are subsequently dried under vacuum at a temperature of about 80 °C.

[0139] Example 3 - Preparation of positive electrode films

[0140] The composition of the positive electrode films is shown in Table 2. Table 2. Composition of the positive electrode films

[0141] *NBR: acrylonitrile-butadiene rubber; SBS: styrene-butadiene-styrene; PB: polybutadiene; PNB: polynorbornene of Formula 11(b). a) Preparation of a positive electrode film (Film 1) 1.55 g of LiNiO particles ,6 Mno ,2 Coo ,2 02(NMC 622) coated with commercially sourced LiNbC>3 having an average diameter of about 4 pm were mixed with 0.40 g of coated Li6PS5CI particles prepared in Example 1(a) having an average diameter 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 vortex mixer.

[0142] 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 resulting mixture was mixed for about 5 minutes using a planetary centrifugal mixer (Thinky Mixer). An additional amount of solvent (p-xylene) was added to the mixture to achieve an optimum coating viscosity of about 10,000 cP. The resulting suspension was coated onto 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. b) Preparation of a positive electrode film (Film 2)

[0143] 1.55 g of LiNbOs-coated NMC 622 particles having an average diameter of about 4 μm were mixed with 0.40 g of coated Ü6PS5CI particles prepared in Example 1(a) having an average diameter of about 200 nm and 0.5 g of carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0144] 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 to achieve an optimum coating viscosity of about 10,000 cP. The resulting suspension was coated onto aluminum foil by a doctor blade coating method to obtain a positive electrode film coated on 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)

[0145] 1.55 g of LiNbC>3 coated NMC 622 particles having an average diameter of about 4 pm were mixed with 0.40 g of coated Ü6PS5CI particles prepared in Example 1(b) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0146] 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. Additional methoxybenzene was added to the mixture to achieve an optimum coating viscosity of about 10,000 cP. The resulting suspension was coated onto aluminum foil by a doctor blade coating method to obtain a positive electrode film coated on a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120 °C for about 5 hours. d) Preparation of a Positive Electrode Film (Movie 4)

[0147] 1.55 g of LiNbOs coated NMC 622 particles having an average diameter of about 4 μm were mixed with 0.40 g of coated Li6PS5CI particles prepared in Example 1(b) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0148] 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 to achieve an optimum viscosity for coating, about 10,000 cP. The resulting suspension was coated onto 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 a positive electrode film (Film 5)

[0149] 1.55 g of LiNbC>3 coated NMC 622 particles having an average diameter of about 4 pm were mixed with 0.40 g of coated Ü6PS5CI particles prepared in Example 1(b) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0150] 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 amount of solvent, methoxybenzene, was added to the mixture to achieve an optimum coating viscosity of about 10,000 cP. The resulting suspension was coated onto aluminum foil by a doctor blade coating method to obtain a positive electrode film coated on 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)

[0151] 1.55 g of LiNbOs coated NMC 622 particles having an average diameter of about 4 μm were mixed with 0.40 g of coated Li6PS5CI particles prepared in Example 1(c) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0152] 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. Additional methoxybenzene was added to the mixture to achieve an optimum coating viscosity of about 10,000 cP. The resulting suspension was coated onto aluminum foil by a doctor blade coating method to obtain a positive electrode film coated on a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120 °C for about 5 hours. g) Preparation of a Positive Electrode Film (Movie 7)

[0153] 1.55 g of LiNbO3-coated NMC 622 particles having an average diameter of about 4 μm were mixed with 0.40 g of coated Ü6PS5CI particles prepared in Example 1(c) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex 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 amount of solvent, methoxybenzene, was added to the mixture to achieve an optimum viscosity for coating, approximately 10,000 cP.The resulting suspension was coated onto an aluminum foil by a doctor blade coating method to obtain a positive electrode film coated on a current collector. The positive electrode film was then dried under vacuum at a temperature of about 120 °C for about 5 hours. h) Preparation of a positive electrode film (Film 8).

[0154] 1.55 g of LiNbOs coated NMC 622 particles having an average diameter of about 4 μm were mixed with 0.40 g of coated Li6PS5CI particles prepared in Example 1(c) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0155] A polymer solution was prepared separately by dissolving 0.035 g of polybutadiene and 0.015 g of 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 amount of solvent, methoxybenzene, was added to the mixture to achieve an optimum viscosity for coating, about 10,000 cP. The resulting suspension was coated onto 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. i) Preparation of a Positive Electrode Film (Movie 9)

[0156] 1.55 g of LiNbC>3 coated NMC 622 particles having an average diameter of about 4 pm were mixed with 0.40 g of coated Ü6PS5CI particles prepared in Example 1(c) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0157] A polymer solution was prepared separately by dissolving 0.030 g of polybutadiene and 0.020 g of 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 amount of solvent, methoxybenzene, was added to the mixture to achieve an optimum coating viscosity of about 10,000 cP. The resulting suspension was coated onto aluminum foil by a doctor blade coating method to obtain a positive electrode film coated on 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 a Positive Electrode Film (Film 10)

[0158] 1.55 g of LiNbOs-coated NMC 622 particles having an average diameter of about 4 μm were mixed with 0.40 g of coated Li6PS5CI particles prepared in Example 1(c) having an average diameter of about 200 nm and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for about 10 minutes using a vortex mixer.

[0159] A polymer solution was prepared separately by dissolving 0.025 g of polybutadiene and 0.025 g of 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 amount of solvent, methoxybenzene, was added to the mixture to achieve an optimum coating viscosity of about 10,000 cP. The resulting suspension was coated onto aluminum foil by a doctor blade coating method to obtain a positive electrode film coated on 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 3(b)

[0160] Morphological studies of different positive electrode films were carried out using a scanning electron microscope (SEM) equipped with a detector equipped with an energy dispersive X-ray spectrometer (EDS).

[0161] Figure 1 shows in (A) an SEM image of the positive electrode film prepared in Example 3(a) (Movie 1), and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of Ni and S elements. The scale bars represent 300 pm and 100 pm, respectively.

[0162] In Figure 1(A), it is possible to observe the presence of waves on the surface of Film 1, after the drying step of 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 (coated Li6PS5CI). Figure 1 also highlights the presence of sulfide 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 allow the solid electrolyte particles to be dispersed.

[0163] Figure 2 shows in (A) an SEM image of the positive electrode film prepared in Example 3(b) (Movie 2), and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of Ni and S elements. Scale bars represent 100 pm.

[0164] In Figure 2(A), it is possible to observe the absence of waves on the surface of Film 2, after the drying step of the positive electrode film. Figure 2(B) confirms the presence of nickel (in green) and sulfur (in red). Figure 2 also highlights the absence of sulfide 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 allows the solid electrolyte particles to be adequately dispersed.

[0165] 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 the analysis of the distribution of Ni and S elements. Scale bars represent 100 pm.

[0166] Figure 3(A) shows the presence of some waves on the surface of Film 3, after the drying step of the positive electrode film. Figure 3(B) confirms the presence of nickel (in green) and sulfur (in red). Figure 3 also highlights the presence of sulfide 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 adequately disperse the solid electrolyte particles.

[0167] Figure 4 shows in (A) an SEM image of the positive electrode film prepared in Example 3(d) (Movie 4), and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of Ni and S elements. Scale bars represent 100 pm.

[0168] Figure 4(A) shows the presence of some waves on the surface of Film 4, after the drying step of the positive electrode film. Figure 4(B) confirms the presence of nickel (in green) and sulfur (in red). Figure 4 also highlights the presence of sulfide 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 allow the solid electrolyte particles to be well dispersed in the electrode material.

[0169] Figure 5 shows in (A) an SEM image of the positive electrode film prepared in Example 3(e) (Movie 5), and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of Ni and S elements. The scale bars represent 100 pm.

[0170] It is possible to observe in Figure 5(A) the absence of waves on the surface of Film 5, and this, after the drying step of 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 sulfide agglomerates on the surface of Film 5. 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 allows to adequately disperse the solid electrolyte particles. Without wishing to be bound by theory, this could be linked to an effect of the use of polynorbornene modified with -COOH groups. The dispersion seems to be substantially favored by this type of group and by the carbon bridge linked to the structure of the polynorbornene itself.Coating sulfide particles with molecules having double or triple bonds appears to substantially improve dispersion via tt-p interactions and / or polar repulsions.

[0171] Figures 6 to 8 show in (A) SEM images of the positive electrode films prepared in Examples 3(g) to 3(i) (Movies 7 to 9), respectively, and in (B) a top-view SEM image of these same films. Scale bars represent 100 pm.

[0172] Figures 6 to 8 show a 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 allows the coated Li6PS5CI particles and the electronically conductive material to be adequately dispersed by tt-p interactions and polar repulsions.

[0173] Example 5 - Electrochemical Properties The electrochemical properties of the positive electrode films prepared in Examples 3(a) to 3(j) were studied. a) Electrochemical Cell Configurations

[0174] The electrochemical cells were assembled according to the following procedure.

[0175] Pellets of 10 mm diameter were taken from the positive electrode films prepared in Examples 3(a) to 3(j). Ceramic-type inorganic solid electrolytes based on sulfides Li6PS5Cl 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 coin cell cases facing 10 mm diameter lithium metal electrodes on copper current collectors. The electrochemical cells were assembled according to the configurations shown in Table 3. Table 3. Electrochemical Cell Configurations b) Behavior of positive electrode films

[0176] 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 to 5 were cycled at a temperature of 50 °C and Cells 6 to 10 were cycled at a temperature of 30 °C. The formation cycle was performed at a constant charge and discharge current of C / 15. Then 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. Finally, the long cycling experiments were performed at a constant charge and discharge current of C / 3.

[0177] Figure 9 shows a graph of discharge capacity (mAh / g) and coulombic efficiency (%) versus cycle number for Cell 1 ( ■) and 2 (A). It can be observed that there is no substantial difference in capacity retention for Cells 1 and 2. Indeed, the curves are substantially superimposed for the 50 °C cycling of Cells 1 and 2.

[0178] Figure 10 shows a graph of the average charge and discharge potential (V) versus the number of cycles for Cells 1 ( ■) and 2 (A). It can be observed that Cell 2 comprising a mixture of polybutadiene and polynorbornene (with -COOH groups) (80:20 by weight) as binder allows 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 discharge stability with the mixture of polybutadiene and polynorbornene (with -COOH groups) (80:20 by weight). Thus, this mixture of polymers ensures a better dispersion of the electrode components and therefore a better ionic and electronic percolation of said components without substantially affecting the charge transfers.

[0179] Figure 11 shows a plot of discharge capacity and coulombic efficiency versus cycle number for Cells 3 (■), 4 (·) and 5 (A). It can be observed that capacity retention at 50 °C and C / 3 is improved when polybutadiene is used in combination with styrene or polynorbornene as a binder. Indeed, Cells 3 and 5 comprising a styrene-butadiene copolymer (styrene-butadiene-styrene (SBS)) and a blend of polybutadiene and polynorbornene, respectively, show improved capacity retention compared to Cell 4 comprising polybutadiene.

[0180] Figure 12 shows a graph of the average potential in charge and discharge as a function of the number of cycles (related to Figure 11) for Cells 3 (■), 4 (·) and 5 (A). It can be observed 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 allows to ensure cohesion in cycling while allowing breathability of the system.

[0181] 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 (★).

[0182] Figure 14 shows a graph of the average charging and discharging potential as a function of the number of cycles related to Figure 13 for Cells 6 (■), 7 (A), 8 (·), 9 (T) and 10 (★).

[0183] The capacity retention in cycling at C / 3 and 30 °C is little impacted by the change of formulation since there is a polymer that can provide a cohesive effect (styrene or polynorbornene). A lower polarization can be observed for the positive electrode film comprising a mixture of polybutadiene and polynorbornene (60:40 by weight) (Film 9) as binder, especially under load. 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 possessing double or triple bonds.The cohesive nature provided by the increase in the rate of polynorbornene vs polybutadiene ensures stability during cycling while maintaining the particles and the contact between these particles, while the polybutadiene absorbs the volume variations of the active material during cycling.

[0184] Several modifications could be made to any of the embodiments described above without departing from the scope of the present invention as contemplated. The references, patents or scientific literature documents referred to in this application are incorporated herein by reference in their entirety and for all purposes.

Claims

DEMANDS 1. A binder composition 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: Formula I in which, R 1 and R 2 are independently and at each occurrence chosen from among a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom and a chlorine atom.

2. Binder composition according to claim 1, wherein the polynorbornene-based polymer is a Formula II polymer: in which, R 1 and R 2are as defined in claim 1, and n is a natural number chosen so that the average molecular weight by mass of the Formula II polymer is between about 10000 g / mol and about 100,000 g / mol, inclusive upper and lower bounds.

3. Binder composition according to claim 2, wherein the mass average molecular weight of the Formula II polymer is between approximately 12,000 g / mol and approximately 85,000 g / mol, or between approximately 15,000 g / mol and approximately 75,000 g / mol, or between about 20,000 g / mol and about 65,000 g / mol, or between about 25,000 g / mol and about 55,000 g / mol, or between about 25,000 g / mol and about 50,000 g / mol, inclusive upper and lower bounds.

4. Binder composition according to any one of claims 1 to 3, wherein R 1 and R 2 are independently and at each occurrence chosen from a hydrogen atom and a -COOH group.

5. Binder composition according to claim 4, wherein R 1 is a group -COOH and R 2 is a hydrogen atom.

6. Binder composition according to claim 4, wherein R 1 and R 2 are both -COOH groups.

7. Binder composition according to any one of claims 1 to 6, wherein the polybutadiene-based polymer is polybutadiene.

8. Binder composition according to any one of claims 1 to 6, wherein the polybutadiene-based polymer is selected from epoxidized polybutadienes.

9. Binder composition according to claim 8, wherein the epoxy-coated polybutadiene comprises repeating units of Formulas III, IV and V: and two terminal hydroxyl groups.

10. Binder composition according to claim 9, wherein the epoxy polybutadiene is of Formula VI: in which, m is a natural number chosen so that the average molecular weight by mass of epoxidized polybutadiene of Formula VI is between about 1000 g / mol and about 1500 g / mol, upper and lower bounds inclusive; and the equivalent weight of epoxy is between about 100 g / mol and about 600 g / mol, upper and lower bounds inclusive.

11. Binder composition according to claim 10, wherein the average molecular weight by mass of epoxidized polybutadiene of Formula VI is about 1300 g / mol.

12. Binder composition according to claim 10 or 11, wherein the equivalent weight of epoxy is between approximately 210 g / mol and approximately 550 g / mol, inclusive.

13. Binder composition according to any one of claims 10 to 12, wherein the epoxy-coated polybutadiene of Formula VI is a Poly bd resin MC600E having a mass average molecular weight of approximately 1300 g / mol and an equivalent epoxy weight of between approximately 400 g / mol and approximately 500 g / mol, inclusive.

14. Binder composition according to any one of claims 10 to 12, wherein the epoxy polybutadiene of Formula VI is a Poly bd resin MC 605E having a mass average molecular weight of about 1300 g / mol and an equivalent epoxide weight between about 260 g / mol and about 330 g / mol, upper and lower bounds inclusive.

15. Binder composition according to any one of claims 1 to 14, wherein the weight ratio of polybutadiene-based polymer to polynorbornene-based polymer is in the range of about 6:1 to about 2:3 inclusive.

16. Binder composition according to claim 15, wherein the weight ratio is within 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 about 4:1 to about 2:3, or about 6:1 to about 1:1, or about 5.5:1 to about 1:1, or about 5:1 to about 1:1, or about 4.5:1 to about 1:1, or about 4:1 to about 1:1, inclusive upper and lower bounds.

17. Binder composition according to claim 16, wherein the weight ratio is within the range of approximately 4:1 to approximately 1:1, inclusive upper and lower bounds.

18. Binder composition according to any one of claims 1 to 17, further comprising at least one solvent.

19. Binder composition according to claim 18, wherein the solvent is an aprotic solvent.

20. Binder composition according to claim 19, wherein the aprotic solvent is 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.

21. Binder composition according to claim 19 or 20, wherein the aprotic polar 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, a mixture comprising m-xylene and THF, a mixture comprising o-xylene and THF, a mixture comprising p-xylene and DEC, a mixture comprising m-xylene and DEC, a mixture comprising o-xylene and DEC, or a mixture comprising toluene and methoxybenzene.

22. Binder composition according to any one of claims 19 to 21, wherein the aprotic polar solvent is THF, or a mixture comprising THF and methoxybenzene.

23. A binder comprising a binder composition as defined in any one of claims 1 to 22.

24. Binder according to claim 23, which is used in an electrode material.

25. An electrode material comprising an electrochemically active material and a binder composition as defined in claims 1 to 22 or a binder as defined in claim 23.

26. Electrode material according to claim 25, wherein the electrochemically active material is selected from a metal oxide, a metal sulfide, a metal oxysulfide, a metal phosphate, a metal fluorophosphate, a metal oxyfluorophosphate, a metal sulfate, a metal halide, a metal fluoride, sulfur, selenium and a combination of at least two of these.

27. Electrode material according to claim 26, wherein the metal of the electrochemically active material is selected 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.

28. Electrode material according to claim 26, in the electrochemically active material further comprises an alkali or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K) and magnesium (Mg).

29. Electrode material according to any one of claims 26 to 28, wherein the electrochemically active material is a metal and lithium oxide.

30. Electrode material according to claim 29, wherein the metal and lithium oxide is a mixed oxide of lithium, nickel, manganese and cobalt (NCM).

31. Electrode material according to any one of claims 26 to 28, wherein the electrochemically active material is a lithium metal phosphate.

32. Electrode material according to claim 31, wherein the lithium metal phosphate is lithium iron phosphate.

33. Electrode material according to claim 25, wherein the electrochemically active material is selected from a non-alkali or non-alkaline-earth metal, an intermetallic compound, a metal oxide, a metal nitride, a metal phosphide, a metal phosphate, a metal halide, a metal fluoride, a metal sulfide, a metal oxysulfide, carbon, silicon (Si), a silicon-carbon composite (Si-C), or silicon dioxide (SiO₂). x ), a silicon-carbon oxide composite (SiO₂) x -C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnO x ), a tin-carbon oxide composite (SnO x-C), and a combination of at least two of these.

34. Electrode material according to any one of claims 25 to 33, wherein the electrochemically active material further comprises a doping element.

35. Electrode material according to any one of claims 25 to 34, wherein the electrochemically active material is in the form of particles.

36. Electrode material according to claim 35, wherein the electrochemically active material particles further comprise a coating material.

37. Electrode material according to claim 36, wherein the coating material is selected from LhSiO₂, LUTisO₂, LiTaO₂, UAO₂, LhO₂-ZrO₂, LiNbO₂, other similar materials, and a combination of at least two of these.

38. Electrode material according to claim 37, wherein the coating material is LiNbO₃.

39. Electrode material according to claim 36, wherein the coating material is an electronically conductive material.

40. Electrode material according to claim 39, wherein the electronically conductive material is carbon.

41. Electrode material according to any one of claims 25 to 40, wherein further comprises an electronically conductive material.

42. Electrode material according to claim 41, wherein the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and a combination of at least two of these.

43. Electrode material according to claim 41 or 42, wherein the electronically conductive material is carbon black.

44. Electrode material according to any one of claims 41 to 43, wherein the surface of said electronically conductive material is grafted with at least one aryl group of Formula VII: Formula VII in which, 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, or more preferably n is 1.

45. Electrode material according to claim 44, wherein the hydrophilic functional group is a carboxylic acid or sulfonic acid functional group.

46. ​​Electrode material according to claim 45, wherein the aryl group of Formula VII is p-benzoic acid or p-benzenesulfonic acid.

47. Electrode material according to any one of claims 25 to 46, further comprising an additive.

48. Electrode material according to claim 47, wherein the additive is selected from ionic conducting materials, inorganic particles, glass or glass-ceramic particles, ceramic particles, nano-ceramics, salts and a combination of at least two of these.

49. Electrode material according to claim 47 or 48, wherein the additive comprises ceramic, glass or glass-ceramic particles based on fluoride, phosphide, sulfide, oxysulfide or oxide.

50. Electrode material according to any one of claims 47 to 49, wherein the additive is selected from compounds of the type LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides, in crystalline and / or amorphous form, and a combination of at least two of these.

51. Electrode material according to any one of claims 47 to 50, wherein the additive is selected from inorganic compounds of formulas: MLZO (for example, M7La3Zr20i2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a >La3Zr(2-b)TabOi2, and M(7- a >La3Zr(2-b)NbbOi2); MLTaO (for example, M7La3Ïa20i2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (for example, M7La3Sn20i2); MAGP (for example, Mi +a Al a Ge2- a (P04)3); MATP (for example, Mi +a Al a TÎ2- a (P04)3,); - MLTiO (for example, M 3a There (2 / 3-a) Ti03); MZP (for example, M a Zrb(P04) c ); MCZP (for example, M a CabZr c (P04)d); MGPS (for example, M a Ge b P c S d such as MioGeP2Si2); MGPSO (for example, M a Ge b P c S d O e ); MSiPS (for example, M a If b P c S d such as M 10 S1P2S 12 ); MSiPSO (for example, M a If b P c S d O e ); MSnPS (for example, M a Sn b P c S d such as MioSnP2Si2); MSnPSO (for example, M a Sn b P c S d O e ); MPS (for example, M a P b S c such as M7P3S 11 ); MPSO (for example, M a P b S c O d ); MZPS (for example, M a Zn b P c S d ); MZPSO (for example, M a Zn b PCS d O e ); - xM2S-yP2S5; - xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; - xM2S-yP2S5-zP205-wMX; - xM2S-yM20-zP2S5; - xM2S-yM20-zP2S5-wMX; - xM2S-yM20-zP2S5-wP205; - xM2S-yM20-zP2S5-wP205-vMX; - xM2S-ySiS2; MPSX (for example, M a P b S c X d such as M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (for example, M a PbS c OdX e ); MGPSX (for example, M a GebP c SdX e ); MGPSOX (for example, M a Ge b P c S d O e X f ); MSiPSX (for example, M a SibP c SdXe); MSiPSOX (for example, M a If b P c S d O e X f ); MSnPSX (for example, M a SnbP c SdXe); MSnPSOX (for example, M a Sn b P c S d O e X f ); MZPSX (for example, M a ZnbP c SdXe); MZPSOX (for example, M a Zn b P c S d O e X f ); - M3OX; - M2HOX; - M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which: M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and in which, when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality; X is chosen from F, Cl, Br, I or a combination of at least two of these; a, b, c, d, e and f are non-zero numbers 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 obtain a stable compound.

52. Electrode material according to claim 51, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and a combination of at least two of these.

53. Electrode material according to claim 52, wherein M is Li.

54. Electrode material according to any one of claims 47 to 53, wherein the additive is selected from argyrodite-type inorganic compounds of formula LiePSsX, in which X is Cl, Br, I or a combination of at least two of these.

55. Electrode material according to any one of claims 47 to 54, wherein the additive is Li6PS5Cl.

56. An electrode comprising the electrode material as defined in any one of claims 25 to 55 on a current collector.

57. A self-supporting electrode comprising the electrode material as defined in any one of claims 25 to 55.

58. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein at least one of the positive or negative electrodes is as defined in claim 56 or 57 or comprises an electrode material as defined in any one of claims 25 to 55.

59. Electrochemical cell according to claim 58, wherein the electrolyte is a liquid electrolyte comprising a salt in a solvent.

60. Electrochemical cell according to claim 58, wherein the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

61. Electrochemical cell according to claim 58, wherein the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

62. Electrochemical cell according to claim 58, wherein the electrolyte is a solid hybrid polymer-ceramic electrolyte.

63. Electrochemical cell according to claim 58, wherein the electrolyte comprises an inorganic solid electrolyte material.

64. Electrochemical cell according to claim 63, wherein the inorganic solid electrolyte material comprises ceramic, glass or glass-ceramic particles based on fluoride, phosphide, sulfide, oxysulfide or oxide.

65. Electrochemical cell according to claim 63 or 64, wherein the inorganic solid electrolyte material is selected from compounds of the type LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskites, oxides, sulfides, oxysulfides, phosphides, fluorides, in crystalline and / or amorphous form, and a combination of at least two of these.

66. Electrochemical cell according to any one of claims 63 to 65, wherein the inorganic solid electrolyte material is selected from inorganic compounds of formulas: MLZO (for example, M7La3Zr20i2, M(7- a) La3Zr2AlbOi2, M(7- a) La3Zr2GabOi2, M(7- a) La3Zr(2-b)TabOi2, and M(7- a) La3Zr(2-b>NbbOi2); MLTaO (for example, M7La3Ïa20i2, M5La3Ta20i2, and M6La3Ta1.5Y0.5O12); MLSnO (for example, M7La3Sn20i2); MAGP (for example, Mi +a Al a Ge2- a (P04)3); MATP (e.g., Mi +a Al a Ti2- a (P04)3,); - MLTiO (e.g., M 3a The (2 / 3-a) Ti03); MZP (e.g., M a Zrb(P04) c ); MCZP (e.g., M a CabZr c (P04)d); MGPS (e.g., M a Here b P c S d such that Mi0GeP2Si2); MGPSO (e.g., M a Here b P c S d OH e ); MSiPS (e.g., M a If b P c S d such that M 10 S1P2S 12 ); MSiPSO (e.g., M a If b P c S d OH e ); MSnPS (e.g., M a Sn b P c S d such as MioSnP2Si2); MSnPSO (e.g., M a Sn b P c S d OH e ); MPS (e.g., Ma P b S c such as M7P3S 11 ); MPSO (for example, M a P b S c O d ); MZPS (for example, M a Zri b PCS d ); MZPSO (for example, M a Zn b P c S d O e ); - xM2S-yP2S5; - xM2S-yP2S5-zMX; xM2S-yP2S5-zP205; - xM2S-yP2S5-zP205-wMX; - xM2S-yM20-zP2S5; - xM2S-yM20-zP2S5-wMX; - xM2S-yM20-zP2S5-wP205; - xM2S-yM20-zP2S5-wP205-vMX; - xM2S-ySiS2; MPSX (for example, M a P b S c X d such as M7P3S 11 X, M7P2S8X, and M6PS5X); MPSOX (for example, M a PbS c OdX e ); MGPSX (for example, M a GebP c SdX e ); MGPSOX (for example, M a Ge b P c S dO e X f ); MSiPSX (for example, M a SibP c SdXe); MSiPSOX (for example, M a If b P c S d O e X f ); MSnPSX (for example, M a SnbP c SdXe); MSnPSOX (for example, M a Sn b P c S d O e X f ); MZPSX (for example, M a ZnbP c SdXe); MZPSOX (for example, M a Zn b PCS d O e X f ); - M3OX; - M2HOX; - M3PO4; M3PS4; and M a PO b N c (where a = 2b + 3c - 5); in which: M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and in which, when M comprises an alkaline earth metal ion, then the number of M is adjusted to achieve electroneutrality; X is chosen from F, Cl, Br, I or a combination of at least two of these; a, b, c, d, e, and f are non-zero numbers 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 obtain a stable compound.

67. Electrochemical cell according to claim 66, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba and a combination of at least two of these.

68. Electrochemical cell according to claim 67, wherein M is Li.

69. Electrochemical cell according to any one of claims 63 to 68, wherein the inorganic solid electrolyte material is selected from argyrodites-type inorganic compounds of formula Li6PS5X, in which X is Cl, Br, I or a combination of at least two of these.

70. An electrochemical cell according to any one of claims 63 to 69, wherein the inorganic solid electrolyte material is LiePSsCI.

71. An electrochemical cell according to any one of claims 58 to 70, wherein the negative electrode comprises an electrochemically active material including an alkali metal, an alkaline earth metal, an alloy comprising at least one alkali or alkaline earth metal, a non-alkaline and non-alkaline earth metal, an alloy, or an intermetallic compound.

72. An electrochemical cell according to claim 71, wherein the electrochemically active material of the negative electrode comprises metallic lithium or an alloy including metallic lithium.

73. Electrochemical cell according to claim 71 or 72, wherein the electrochemically active material of the negative electrode is in the form of a film having a thickness in the range of about 5 pm to about 500 pm, inclusive of upper and lower terminals.

74. Electrochemical cell according to claim 73, wherein the thickness of the film of electrochemically active material of the negative electrode is included in the range from about 10 miti to about 100 miti, including upper and lower bounds.

75. Electrochemical cell according to any one of claims 58 to 70, wherein the positive electrode is pre-lithiumized and the negative electrode is substantially lithium-free.

76. Electrochemical cell according to any one of claims 75, wherein the negative electrode is lithiated in situ during the cycling of said electrochemical cell.

77. An electrochemical accumulator comprising at least one electrochemical cell as defined in any one of claims 58 to 76.

78. Electrochemical accumulator according to claim 77, wherein said electrochemical accumulator is a battery selected from a lithium battery, a lithium-ion battery, a sodium battery, a sodium-ion battery, a magnesium battery, and a magnesium-ion battery.

79. Electrochemical accumulator according to claim 78, wherein said battery is a lithium battery or a lithium-ion battery.

80. Electrochemical accumulator according to claim 78, wherein said electrochemical accumulator is a so-called all-solid battery.

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