Electrode binders comprising blends of polybutadiene-based polymers and polynorbornene-based polymers, electrodes comprising same and their use in electrochemistry - Patents.com

Abstract

The present technology relates to binder compositions and binders for use in electrochemical applications, particularly in electrochemical storage cells such as all-solid-state batteries, comprising blends comprising polybutadiene-based polymers and polynorbornene-based polymers comprising norbornene-based monomer units derived from polymerization of optionally substituted norbornene-based monomers. Electrode materials comprising said binders or binder compositions, and their use in electrochemical cells, for example in electrochemical storage cells, particularly in all-solid-state batteries, are also described.

Description

[Technical field]

[0001] Related Applications This application claims priority under applicable law to Canadian Provisional Patent Application No. 3,120,992, filed June 3, 2021, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Technical Field This application relates to the field of polymers and their use in electrochemical applications. More specifically, this application relates to the field of polymer binders, electrode materials containing them, their manufacturing methods, and their use in electrochemical cells, in particular in all-solid-state batteries. [Background technology]

[0003] background 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.

[0004] 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, a solid electrolyte, and optionally an electronically conductive material, all of which form a monolithic unit.

[0005] One of the key elements of an all-solid-state electrochemical system is the dispersion of each of its components. Indeed, the solid elements may tend to agglomerate during the step of mixing with the binder, which may render the electrode material inhomogeneous. Among the strategies used to solve this problem, the inventors have found the encapsulation of the particles of the different components of the system by a coating material to improve their dispersion. These dispersion problems can also be significantly reduced by the use of binders, additives or dispersing media that improve particle dispersion.

[0006] Norbornene-based polymers are described as additives in published PCT patent application WO2020 / 061710 (Daigle et al.), which are added to polymer binders. Polynorbornene is added to inhibit or reduce parasitic reactions, such as the formation of lithium fluoride (LiF) and hydrofluoric acid (HF) resulting from the decomposition of carbon-fluorine (CF) bonds.

[0007] Korean patent published under KR10-2193945 and PCT patent application published under WO2019 / 004714 describe a method for producing a solid electrolyte film comprising a sulfide-based solid electrolyte, as well as a composite electrode film that allows for improved dispersion, density, and ionic conductivity between solid electrolyte particles, and between solid electrolyte particles and active material particles, by crystallization from an amorphous to a crystalline state. To do this, norbornene-based copolymers are used, in particular poly(ethylene-co-propylene-co-5-methylene-2-norbornene (PEPMNB). However, there remains a need for the development of new materials for use in all-solid-state electrochemical systems with improved properties. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2020 / 061710 [Patent Document 2] Korean Patent Application Publication No. 10-2193945 [Patent Document 2] International Publication No. 2019 / 004714 Summary of the Invention [Means for solving the problem]

[0009] overview According to one embodiment, the present technology provides a method for producing a polybutadiene-based polymer comprising: [ka] (In the formula, R 1 and R 2 is independently selected at each occurrence from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom, and a chlorine atom. and a polynorbornene-based polymer comprising norbornene-based monomer units derived from the polymerization of a compound of the formula (I).

[0010] In one embodiment, the polynorbornene-based polymer has Formula II: [ka] (In the formula, R 1 and R 2 is as defined herein; n is an integer selected such that the weight average molecular weight of the polymer of formula II is from about 10,000 g / mol to about 100,000 g / mol, inclusive. It is a polymer of.

[0011] In another embodiment, the weight average molecular weight of the polymer of Formula II is from about 12,000 g / mol to about 85,000 g / mol, or from about 15,000 g / mol to about 75,000 g / mol, or from about 20,000 g / mol to about 65,000 g / mol, or from about 25,000 g / mol to about 55,000 g / mol, or from about 25,000 g / mol to about 50,000 g / mol, inclusive.

[0012] In another embodiment, R 1 and R 2 is independently selected at each occurrence from a hydrogen atom and a -COOH group. 1 is a -COOH group, and R 2 is a hydrogen atom. 1 and R 2are both -COOH groups.

[0013] In another embodiment, the polybutadiene-based polymer is polybutadiene.

[0014] In another embodiment, the polybutadiene-based polymer is selected from epoxidized polybutadienes. According to one example, the epoxidized polybutadienes are represented by Formulae III, IV, and V: [ka] repeating units, as well as two hydroxyl end groups.

[0015] According to another example, the epoxidized polybutadiene can be represented by formula VI: [ka] (In the formula, m is an integer selected such that the weight average molecular weight of the epoxidized polybutadiene of formula VI is from about 1000 g / mol to about 1500 g / mol, inclusive. of; The epoxide equivalent weight is from about 100 g / mol to about 600 g / mol, inclusive.

[0016] According to another example, the epoxidized polybutadiene is Poly bd™ 600E resin having a weight average molecular weight of about 1300 g / mol and an epoxide equivalent weight of about 400 g / mol to about 500 g / mol, inclusive.

[0017] According to another example, the epoxidized polybutadiene is Poly bd™ 605E resin having a weight average molecular weight of about 1300 g / mol and an epoxide equivalent weight of about 260 g / mol to about 330 g / mol, inclusive.

[0018] 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, inclusive. In accordance with the intended variation, the weight ratio is in the range of about 4:1 to about 1:1, inclusive.

[0019] According to another aspect, the present technology relates to a binder comprising the binder composition defined herein. According to an example, the binder is used in an electrode material.

[0020] According to another aspect, the present technology relates to an electrode material comprising an electrochemically active material and a binder as defined herein.

[0021] In some embodiments, the electrochemically active material is selected from metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, metal halides, metal fluorides, sulfur, selenium, and combinations 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 combinations of at least two thereof. According to some examples, the electrochemically active material further comprises an alkali metal or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K), and magnesium (Mg).

[0022] In certain embodiments, the electrochemically active material is 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), a silicon oxide (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and a combination of at least two thereof.

[0023] In another embodiment, the electrochemically active material further comprises a doping element.

[0024] In another embodiment, the electrochemically active material is in the form of particles. For example, the particles of the electrochemically active material additionally include a coating material. According to one example, the coating material is Li2SiO3, Li4Ti5O 12 , LiTaO3, LiAlO2, Li2O-ZrO2, LiNbO3, other similar materials, and combinations of at least two thereof. According to another example, the coating material is an electronically conductive material.

[0025] 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 fiber, carbon nanofiber, carbon nanotube, and combinations of at least two thereof. According to an example of interest, the surface of the electronically conductive material is provided with a cation bond represented by Formula VII: [ka] (In the formula, FG is a hydrophilic functional group; n is an integer in the range of 1 to 5, preferably n is in the range of 1 to 3, preferably n is 1 or 2, or more preferably n is 1. is grafted with at least one aryl group.

[0026] According to one example, the hydrophilic functional group is a carboxylic acid functional group or a sulfonic acid functional group. According to another example, the aryl group of formula VII is p-benzoic acid or p-benzenesulfonic acid.

[0027] In another embodiment, the electrode material further comprises an additive. For example, the additive is selected from ion-conducting materials, inorganic particles, glass or glass-ceramic particles, ceramic particles, nanoceramics, salts, and combinations of at least two thereof. According to an example, the additive comprises ceramic, glass, or glass-ceramic particles based on fluorides, phosphides, sulfides, oxysulfides, or oxides. According to another example, the additive is selected from LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and combinations of at least two thereof, in crystalline and / or amorphous form. According to another example, the additive is selected from a compound of the formula MLZO (e.g., M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 , and M. (7-a) La3Zr (2-b) Nb b O 12 );MLTaO (e.g., M7La3Ta2O 12 , M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO (e.g., M7La3Sn2O 12 );MAGP(e.g., M 1+a Al a Ge 2-a (PO4)3); MATP (e.g., M 1+a Al a Ti2-a (PO4)3);MLTiO (e.g., M 3a La (2 / 3-a) TiO3);MZP (e.g., M a Zr b (PO4) c );MCZP (e.g., M a Ca b Zr c (PO4) d );MGPS(e.g., M 10 GeP2S 12 M a Ge b P c S d );MGPSO(e.g., M a Ge b P c S d O e ); MSiPS (e.g., M 10 SiP2S 12 M a S b P c S d );MSiPSO (e.g., M a S b P c S d O e ); MSnPS (e.g., M 10 SnP2S 12 M a Sn b P c S d );MSnPSO (e.g., M a Sn b P c S d O e );MPS(e.g., M7P3S 11 M a P b S c );MPSO (e.g., M a P b S c O d );MZPS(e.g., M a Zinc b P c S d );MZPSO(e.g., M a Zinc bP c S d O e );xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5;xM2S- yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example, M7P3S 11 X, M7P2S8X and M6PS5X a P b S c X d );MPSOX(For example, M a P b S c O 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 O e X f );MSiPSX(e.g., M a S b P c S d X e );MSiPSOX(e.g., M a S 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., M a Sn b P c S d O e X f );MZPSX(For example, M a Zinc b P c Sd X e );MZPSOX(For example, M a Zinc b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c (wherein a=2b+3c-5); (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and when M comprises an alkaline earth metal ion, the number of M's 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 non-zero numbers and are independently selected in each formula to achieve electroneutrality; v, w, x, y and z are non-zero numbers, independently selected in each formula to obtain a stable compound. The inorganic compounds are selected from the group consisting of:

[0028] According to a variant of interest, the additive is selected from inorganic argyrodite type compounds of formula Li6PS5X, where X is Cl, Br, I or a combination of at least two of them. For example, the additive is Li6PS5Cl.

[0029] According to another aspect, the present technology relates to an electrode comprising the electrode material defined herein on a current collector. According to another aspect, the present technology relates to a free-standing electrode comprising the electrode material defined herein.

[0030] According to 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 defined herein.

[0031] In another embodiment, the electrolyte is a liquid electrolyte comprising a salt in a solvent.

[0032] In another embodiment, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer.

[0033] In another embodiment, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer.

[0034] In another embodiment, the electrolyte is a polymer-ceramic hybrid solid electrolyte.

[0035] In another embodiment, the electrolyte comprises an inorganic solid electrolyte material. According to an example, the inorganic solid electrolyte material comprises ceramic, glass, or glass-ceramic particles based on fluorides, phosphides, sulfides, oxysulfides, or oxides. According to another example, the inorganic solid electrolyte material is selected from LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and combinations of at least two thereof, in crystalline and / or amorphous form. According to another example, the inorganic solid electrolyte material is a material having the formula MLZO (e.g., M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 , and M. (7-a) La3Zr (2-b) Nb b O 12 );MLTaO (e.g., M7La3Ta2O 12 , M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO (e.g., M7La3Sn2O 12 );MAGP(e.g., M 1+aAl a Ge 2-a (PO4)3); MATP (e.g., M 1+a Al a Ti 2-a (PO4)3);MLTiO (e.g., M 3a La (2 / 3-a) TiO3);MZP (e.g., M a Zr b (PO4) c );MCZP (e.g., M a Ca b Zr c (PO4) d );MGPS(e.g., M 10 GeP2S 12 M a Ge b P c S d );MGPSO(e.g., M a Ge b P c S d O e ); MSiPS (e.g., M 10 SiP2S 12 M a S b P c S d );MSiPSO (e.g., M a S b P c S d O e ); MSnPS (e.g., M 10 SnP2S 12 M a Sn b P c S d );MSnPSO (e.g., M a Sn b P c S d O e );MPS(e.g., M7P3S 11 M a P b S c );MPSO (e.g., M a P b S c O d );MZPS(e.g., M a Zincb P c S d );MZPSO(e.g., M a Zinc b P c S d O e );xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5;xM2S- yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example, M7P3S 11 X, M7P2S8X and M6PS5X a P b S c X d );MPSOX(For example, M a P b S c O 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 O e X f );MSiPSX(e.g., M a S b P c S d X e );MSiPSOX(e.g., M a S 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., M a Sn b P c S d O eX f );MZPSX(For example, M a Zinc b P c S d X e );MZPSOX(For example, M a Zinc b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c (wherein a=2b+3c-5); (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and when M comprises an alkaline earth metal ion, the number of M's 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 non-zero numbers and are independently selected in each formula to achieve electroneutrality; v, w, x, y and z are non-zero numbers, independently selected in each formula to obtain a stable compound. The inorganic compounds are selected from the group consisting of:

[0036] According to a variant of interest, the inorganic solid electrolyte material is selected from argyrodite-type inorganic compounds of the formula Li6PS5X, where X is Cl, Br, I, or a combination of at least two thereof. For example, the inorganic solid electrolyte material is Li6PS5Cl.

[0037] According to another aspect, the present technology relates to an electrochemical storage battery comprising at least one electrochemical cell as defined herein.

[0038] 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, and a magnesium ion battery.

[0039] In another embodiment, the electrochemical storage battery is an all-solid-state battery. [Brief description of the drawings]

[0040] [Figure 1] 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 μm and 100 μm, respectively.

[0041] [Diagram 2] 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 bar represents 100 μm.

[0042] [Diagram 3] 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 bar represents 100 μm.

[0043] [Figure 4] 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 bar represents 100 μm.

[0044] [Diagram 5]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 bar represents 100 μm.

[0045] [Figure 6] 6 shows in (A) an SEM image of film 7 which makes it possible to observe the different layers of the film, and in (B) a top-view SEM image of the same film, as described in Example 4. The scale bar represents 100 μm.

[0046] [Figure 7] 7 shows in (A) an SEM image of film 8 which makes it possible to observe the different layers of the film, and in (B) a top-view SEM image of the same film, as described in Example 4. The scale bar represents 100 μm.

[0047] [Figure 8] 8 shows in (A) an SEM image of film 9 which makes it possible to observe the different layers of the film, and in (B) a top-view SEM image of the same film, as described in Example 4. The scale bar represents 100 μm.

[0048] [Figure 9] FIG. 9 shows graphs of discharge capacity (mAh / g) and coulombic efficiency (%) as a function of cycle number for Cell 1 (squares) and Cell 2 (triangles) described in Example 5(b).

[0049] [Figure 10] FIG. 10 shows a graph of the average charge and discharge potential (V) as a function of cycle number for Cell 1 (squares) and Cell 2 (triangles) described in Example 5(b).

[0050] [Figure 11]FIG. 11 shows graphs of discharge capacity (mAh / g) and coulombic efficiency (%) as a function of cycle number for Cell 3 (squares), Cell 4 (circles), and Cell 5 (triangles) described in Example 5(b).

[0051] [Figure 12] FIG. 12 shows a graph of the average charge and discharge potential (V) as a function of cycle number for Cell 3 (squares), Cell 4 (circles), and Cell 5 (triangles) described in Example 5(b).

[0052] [Figure 13] FIG. 13 shows graphs of discharge capacity and coulombic efficiency (%) as a function of cycle number for Cell 6 (squares), Cell 7 (triangles), Cell 8 (circles), Cell 9 (inverted triangles), and Cell 10 (stars) described in Example 5(b).

[0053] [Figure 14] FIG. 14 shows a graph of the average charge and discharge potential (V) as a function of cycle number for Cell 6 (squares), Cell 7 (triangles), Cell 8 (circles), Cell 9 (inverted triangles), and Cell 10 (stars), as described in Example 5(b). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0054] Detailed Description All technical and scientific terms and expressions used herein have the same definitions as commonly understood by those skilled in the art. However, definitions of some of the terms and expressions used are provided below.

[0055] When the term "about" is used herein, it means approximately, within a range, or approximately.For example, when the term "about" is used in relation to a numerical value, it modifies the numerical value up or down by a variation of 10% from its nominal value.This term may also take into account, for example, experimental error or rounding of the measuring device.

[0056] When a range of values ​​is recited in this application, the lower and upper limits of the range are always included within the definition, unless otherwise indicated. When a range of values ​​is recited in this application, all intervening ranges and subranges, as well as individual values ​​that fall within the range of values, are included within the definition.

[0057] When the article "a" is used to introduce an element in this application, it does not mean "only one," but rather "one or more." Of course, when the description states that a particular step, component, element, or feature "may" be included or "can" be included, that particular step, component, element, or feature need not be included in every embodiment.

[0058] For greater clarity, the phrase "monomer unit derived from" and equivalent phrases, as used herein, refer to a repeating polymer unit resulting from the polymerization of a polymerizable monomer.

[0059] The term "aryl" as used herein refers to a substituted or unsubstituted aromatic ring, where the contributing atoms allow for the formation of a single ring or multiple fused rings. Representative aryl groups include groups having 6 to 14 ring members. For example, aryl can include phenyl, naphthyl, and the like. The aromatic ring may be substituted at one or more ring positions with, for example, carboxyl (-COOH) or sulfonic acid (-SO3H) groups, amine groups, and other similar groups.

[0060] The expression "hydrophilic functional group" as used herein refers to a functional group that is attracted to water molecules. Hydrophilic functional groups can generally be charged and / or capable of forming hydrogen bonds. Non-limiting examples of hydrophilic functional groups include hydroxyl, carboxyl, sulfonic acid, phosphate, amine, amide, and other similar groups. This expression further includes salts of these groups, where applicable.

[0061] The expression "free-standing electrode" as used herein refers to an electrode without a metal current collector.

[0062] The chemical structures described herein are drawn according to conventions in the art, and when an atom, such as a drawn carbon atom, appears to contain incomplete valences, the valences are considered to be satisfied by one or more hydrogen atoms even if no hydrogen atoms are explicitly drawn.

[0063] The present technology relates to electrode binders comprising blends of polymers, and more particularly to electrode binders comprising blends of polymers for use in all-solid-state electrochemical systems.

[0064] More specifically, the present technology provides a method for producing a polybutadiene-based polymer comprising: [ka] (In the formula, R 1 and R 2 is independently selected at each occurrence from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom, and a chlorine atom. and a polynorbornene-based polymer comprising norbornene-based monomer units derived from the polymerization of a compound of the formula (I).

[0065] According to one example, R 1 or R 2 is selected from -COOH, -SOH, -OH, -F, and -Cl, which is 1 or R 2 means that at least one of the groups is different from a hydrogen atom.

[0066] According to another example, R 1 is a -COOH group, and R 2 is a hydrogen atom.

[0067] According to another example, R1 or R 2 At least one of R is a -COOH group and the norbornene-based monomer unit is a carboxylic acid functionalized norbornene-based monomer unit. 1 is a -COOH group, and R 2 is a hydrogen atom. According to another variant of the invention, R 1 and R 2 are both -COOH groups. The present technology comprises a polybutadiene-based polymer and a copolymer of Formula II: [ka] (In the formula, R 1 and R 2 is as defined above, and n is an integer selected such that the weight average molecular weight of the polymer of formula II is from about 10,000 g / mol to about 100,000 g / mol, inclusive, as determined by gel permeation chromatography (GPC). and a polynorbornene-based polymer of the present invention.

[0068] According to another example, the weight average molecular weight of the polynorbornene-based polymer of formula II is from about 12,000 g / mol to about 85,000 g / mol, or from about 15,000 g / mol to about 75,000 g / mol, or from about 20,000 g / mol to about 65,000 g / mol, or from about 25,000 g / mol to about 55,000 g / mol, or from about 25,000 g / mol to about 50,000 g / mol, inclusive of upper and lower limits, as determined by GPC.

[0069] According to the transformation of the purpose, R 1 and R 2 is a -COOH group.

[0070] According to another example, the polynorbornene-based polymer may be represented by Formula II(a): [ka] (In the formula, R 2 and n is as defined above. It is a polymer of. According to another example, the polynorbornene-based polymer may be represented by Formula II(b): [ka] (In the formula, n is as defined above) It is a polymer of.

[0071] According to another example, the polynorbornene-based polymer of formula II, II(a), or II(b) is a homopolymer.

[0072] According to another example, the polymerization of the norbornene-based monomers of formula I can be carried out by any known suitable polymerization method. According to a variant of the invention, the polymerization of the compounds of formula I can be carried out according to the method of Commarieu, B. et al. ("Ultrahigh T g Polymerization of the compounds of formula I may also be carried out by the synthesis process described in "Epoxy Thermosets Based on Insertion Polynorbornenes", Macromolecules, 49.3 (2016): 920-925). For example, polymerization of the compounds of formula I may also be carried out by an addition polymerization process.

[0073] For example, polynorbornene-based polymers produced by addition polymerization processes can be substantially stable under harsh 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 temperatures (T g ) may be equal to or greater than about 300°C, for example, as high as 350°C.

[0074] According to another example, the polybutadiene-based polymer may have a substantially higher elasticity or flexibility and / or a substantially lower glass transition temperature (T) than that of the polynorbornene-based polymer of Formula II, II(a), or II(b). g )

[0075] According to another example, the polybutadiene-based polymer may be polybutadiene. Alternatively, the polybutadiene-based polymer may be a functionalized polybutadiene or polybutadiene-derived polymer. For example, compared to non-functionalized polybutadiene, the functionalized polybutadiene or polybutadiene-derived polymer may have a substantially higher elasticity or flexibility and / or a substantially lower glass transition temperature (T g ) and / or may improve the mechanical or adhesive properties of the electrode binder.

[0076] According to another example, the polybutadiene-based polymer is selected from epoxidized polybutadienes, such as epoxidized polybutadienes having reactive end groups. For example, the reactive end groups may be hydroxyl groups. The epoxidized polybutadienes may be represented by formulae III, IV, and V: [ka] repeat unit, as well as two hydroxyl end groups.

[0077] By way of another example, the weight average molecular weight of the epoxidized polybutadiene containing repeating units of formulas III, IV, and V may be from about 1000 g / mol to about 1500 g / mol, inclusive, as determined by GPC.

[0078] According to another example, the epoxide equivalent weight of an epoxidized polybutadiene containing repeating units of formulae III, IV, and V is from about 100 g / mol to about 600 g / mol, inclusive, as determined by GPC. The epoxide equivalent weight corresponds to the mass of the resin containing one mole of epoxide functional groups.

[0079] According to a variant of the subject matter, the epoxidized polybutadiene has the formula VI: [ka] (In the formula, m is an integer selected such that the weight average molecular weight of the epoxidized polybutadiene of formula VI is from about 1000 g / mol to about 1500 g / mol, inclusive, as determined by GPC. The The epoxide equivalent weight is from about 100 g / mol to about 600 g / mol, inclusive, as determined by GPC.

[0080] According to another example, the weight average molecular weight of the epoxidized polybutadiene comprising repeat units of formula III, IV and V, or of the epoxidized polybutadiene of formula VI, is from about 1050 g / mol to about 1450 g / mol, or from about 1100 g / mol to about 1400 g / mol, or from about 1150 g / mol to about 1350 g / mol, or from about 1200 g / mol to about 1350 g / mol, or from about 1250 g / mol to about 1350 g / mol, inclusive, as determined by GPC. According to a variant of interest, the weight average molecular weight of the epoxidized polybutadiene comprising repeat units of formula III, IV and V, or of the epoxidized polybutadiene of formula VI, is about 1300 g / mol, as determined by GPC.

[0081] According to another example, the epoxide equivalent weight of the epoxidized polybutadiene comprising repeat units of formula III, IV and V, or of the epoxidized polybutadiene of formula VI, is from about 150 g / mol to about 550 g / mol, or from about 200 g / mol to about 550 g / mol, or from about 210 g / mol to about 550 g / mol, or from about 260 g / mol to about 500 g / mol, inclusive, as determined by GPC. According to a variant of interest, the epoxide equivalent weight of the epoxidized polybutadiene comprising repeat units of formula III, IV and V, or of the epoxidized polybutadiene of formula VI, is from about 400 g / mol to about 500 g / mol, or from about 260 g / mol to about 330 g / mol, inclusive, as determined by GPC.

[0082] For example, the epoxidized polybutadiene of formula VI is a commercially available hydroxyl-terminated epoxidized polybutadiene resin of the Poly bd™ 600E or 605E type sold by Cray Valley. The physicochemical properties of these resins are presented in Table 1. [Table 1]

[0083] It is understood that the electrode binder comprises a polymer blend including at least one first polymer and at least one second polymer, where the first polymer is a polybutadiene-based polymer and the second polymer is a polynorbornene-based polymer including norbornene-based monomer units derived from the polymerization of a compound of formula I, or a polymer of formula II, II(a), or II(b).

[0084] According to another example, the "first polymer:second polymer" ratio is within the range of about 6:1 to about 2:3, inclusive. For example, the "first polymer:second polymer" 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, inclusive. According to a variant of interest, the "first polymer:second polymer" ratio is within the range of about 4:1 to about 1:1, inclusive.

[0085] According to another example, the polymer blend of the electrode binder may be solubilized in at least one solvent. For example, the solvent may be selected for its ability to solubilize and efficiently mix with the polymer blend. For example, the solvent may be an organic solvent, such as 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 miscible combinations of at least two thereof. According to variants 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, said solvent is preferably removed from the electrode in which the binder is found, before it is assembled with the other elements of the electrochemical cell.

[0086] The present technology also relates to the use of an electrode binder as defined herein in an electrode material. Indeed, an electrode material comprising an electrochemically active material and an electrode binder as defined herein is also contemplated.

[0087] According to an example, the electrode material defined herein further comprises an electronically conductive material.Non-limiting examples of electronically conductive materials include carbon sources such as carbon black (e.g., Ketjen™ carbon and Super P™ carbon), acetylene black (e.g., Shawinigan carbon and Denka™ carbon black), graphite, graphene, carbon fibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanofibers, carbon nanotubes (CNTs), and combinations of at least two thereof.

[0088] By way of another example, the electronically conductive material, when present in the electrode material, may be a modified electronically conductive material, such as those described in PCT published patent application WO2019 / 218067 (Delaporte et al.). For example, the modified electronically conductive material may be a compound represented by Formula VII: [ka] (In the formula, FG is a hydrophilic functional group; n is an integer ranging from 1 to 5, preferably n is in the range of 1 to 3, preferably n is 1 or 2, or more preferably n is 1. may be grafted with at least one aryl group of

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

[0090] According to a variant of the subject matter, the electronically conductive material is carbon black, optionally grafted with at least one aryl group of formula VII. According to another variant of the subject matter, 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 fiber (e.g., vapor-grown carbon fiber (VGCF)), carbon nanofiber, carbon nanotube (CNT), or a combination of at least two thereof.

[0091] According to another example, the electrode material is a positive electrode material, and the electrochemically active material is selected from metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, metal halides (e.g., metal fluorides), sulfur, selenium, and combinations 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, if appropriate. The electrochemically active material may further include an alkali metal or alkaline earth metal, such as lithium (Li), sodium (Na), potassium (K), or magnesium (Mg), as required.

[0092] Non-limiting examples of electrochemically active materials include lithium metal phosphates, complex oxides such as LiM'PO4 (wherein M' is Fe, Ni, Mn, Co, or combinations thereof), LiV3O8, VO5, LiMn2O4, LiM''O2 (wherein M'' is Mn, Co, Ni, or combinations thereof), Li(NiM''')O2 (wherein M''' is Mn, Co, Al, Fe, Cr, Ti, or Zr, or combinations thereof), and combinations thereof, where suitable.

[0093] According to one example of interest, the electrochemically active material is an oxide or a phosphate as described above.

[0094] For example, the electrochemically active material is lithium manganese oxide, where the manganese may be partially replaced by a second transition metal, such as lithium nickel manganese cobalt oxide (NMC). According to one alternative, the electrochemically active material is a lithiated iron phosphate. According to another alternative, the electrochemically active material is a manganese-containing lithiated metal phosphate, such as those described above, for example, the manganese-containing lithiated metal phosphate is lithiated iron and manganese phosphate (LiMn 1-x Fe x PO4; in which x is 0.2 to 0.5.

[0095] According to another example, the electrode material is a negative electrode material, and the electrochemically active material is selected from the group consisting of non-alkali and non-alkaline earth metals (e.g., indium (In), germanium (Ge), and bismuth (Bi)), intermetallic compounds (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, expanded graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxides (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x For example, the metal oxide is selected from the group consisting of the formula M"" b O cwhere M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; b and c are numbers such that the ratio c:b is in the range of 2 to 3 (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM''''O where M'''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination of at least two thereof (e.g., lithium titanate (Li4Ti5O 12 ) or lithium molybdenum oxide (Li2Mo4O 13 The compound may be selected from the following:

[0096] According to another example, the electrochemically active material may be doped with small amounts of other inclusion elements, if necessary, for example to adjust or optimize its electrochemical properties. The electrochemically active material may be doped by partial replacement of metals with other ions. For example, the electrochemically active material may be doped with transition metals (e.g., Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, or Y) and / or metals other than transition metals (e.g., Mg, Al, or Sb).

[0097] According to another example, the electrochemically active material may be in the form of particles (e.g., microparticles and / or nanoparticles), which may be newly formed or may be from a commercial source. For example, the electrochemically active material may be in the form of particles coated with a layer of a coating material in a core-shell configuration. The coating material may be an electronically conductive material, e.g., a conductive carbon coating. The conductive carbon layer may also be grafted with at least one aryl group of formula VII, if desired. Alternatively, the coating material may be capable of substantially reducing the interfacial reaction at the interface between the electrochemically active material and the electrolyte, e.g., a solid electrolyte, in particular a sulfide-based ceramic-type solid electrolyte (e.g., Li6PS5Cl-based). For example, the coating material may be Li2SiO3, Li4Ti5O 12, LiTaO3, LiAlO2, Li2O-ZrO2, LiNbO3, combinations thereof where appropriate, and other similar materials. According to a variant of the invention, the coating material comprises LiNbO3.

[0098] According to another example, the electrode material defined herein further comprises an additive. For example, the additive is selected from ion-conducting materials, inorganic particles, glass or glass-ceramic particles, ceramic particles including nanoceramics (e.g., Al2O3, TiO2, SiO2, and other similar compounds), salts (e.g., lithium salts), and combinations of at least two of them. For example, the additive may be an ion conductor selected from LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite-type compounds, oxides, sulfides, sulfur halides, phosphates, thiophosphates, and combinations of at least two of them, in crystalline and / or amorphous form.

[0099] According to the variant of interest, the additive, when present in the electrode material, may be a ceramic, glass, or glass-ceramic particle in crystalline and / or amorphous form. For example, the ceramic, glass, or glass-ceramic particle may be fluoride, phosphide, sulfide, oxysulfide, oxide-based, or a combination of at least two thereof. Non-limiting examples of ceramic, glass, or glass-ceramic particles include those of the formula MLZO (e.g., M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 , and M. (7-a) La3Zr (2-b) Nb b O 12 );MLTaO (e.g., M7La3Ta2O 12 , M5La3Ta2O 12, and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO (e.g., M7La3Sn2O 12 );MAGP(e.g., M 1+a Al a Ge 2-a (PO4)3); MATP (e.g., M 1+a Al a Ti 2-a (PO4)3);MLTiO (e.g., M 3a La (2 / 3-a) TiO3);MZP (e.g., M a Zr b (PO4) c );MCZP (e.g., M a Ca b Zr c (PO4) d );MGPS(e.g., M 10 GeP2S 12 M a Ge b P c S d );MGPSO(e.g., M a Ge b P c S d O e ); MSiPS (e.g., M 10 SiP2S 12 M a S b P c S d );MSiPSO (e.g., M a S b P c S d O e ); MSnPS (e.g., M 10 SnP2S 12 M a Sn b P c S d );MSnPSO (e.g., M a Sn b P c S d O e );MPS(e.g., M7P3S 11 M a Pb S c );MPSO (e.g., M a P b S c O d );MZPS(e.g., M a Zinc b P c S d );MZPSO(e.g., M a Zinc b P c S d O e );xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5;xM2S- yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example, M7P3S 11 M such as X, M7P2S8X, and M6PS5X a P b S c X d ;MPSOX (e.g., M a P b S c O 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 O e X f );MSiPSX(e.g., M a S b P c S d X e );MSiPSOX(e.g., M a S b P c S d O e X f );MSnPSX (e.g., M a Sn b Pc S d X e );MSnPSOX (e.g., M a Sn b P c S d O e X f );MZPSX(For example, M a Zinc b P c S d X e );MZPSOX(For example, M a Zinc b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c (wherein a=2b+3c-5); (In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and when M comprises an alkaline earth metal ion, the number of M's 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 non-zero numbers and are independently selected in each formula to achieve electroneutrality; v, w, x, y and z are non-zero numbers, independently selected in each formula to obtain a stable compound. Examples of inorganic compounds include:

[0100] For example, M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and combinations of at least two of them. According to a variant of interest, M includes Li and may further include at least one of Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and combinations of at least two of them. According to a variant of interest, M includes Na, K, Mg, or combinations of at least two of them.

[0101] For example, the additive, when present in the electrode material, may be a sulfide-based ceramic particle, for example an argyrodite-type ceramic particle of formula Li6PS5X, where X is Cl, Br, I, or a combination of at least two thereof. According to a variant of interest, the additive is argyrodite Li6PS5Cl.

[0102] For example, the method for preparing the electrode material defined herein further includes the use of a solvent, e.g., an organic solvent. For example, the solvent may provide an optimal viscosity for coating the electrode material of about 10,000 cP, and may be substantially removed in a drying step after coating. For example, the solvent may be THF or methoxybenzene (or anisole).

[0103] The present technology also relates to an electrode comprising the electrode material defined herein. According to an example, the electrode may be on a current collector (e.g., aluminum foil or copper foil). Alternatively, the electrode may be a free-standing electrode.

[0104] 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.

[0105] According to a variant of interest, the negative electrode is as defined herein. For example, the electrochemical negative electrode material may be selected for its electrochemical compatibility with the different elements of the electrochemical cell defined herein. For example, the electrochemically active material of the negative electrode material may have a substantially lower redox potential than that of the electrochemically active material of the positive electrode.

[0106] According to another variant of the object, the positive electrode is as defined herein and the negative electrode comprises an electrochemically active material selected from all known compatible electrochemically active materials. For example, the electrochemically active material of the negative electrode may be selected for its electrochemical compatibility with the different elements of the electrochemical cell defined herein. Non-limiting examples of electrochemically active materials of the negative electrode include alkali metals, alkaline earth metals, alloys containing at least one alkali metal or alkaline earth metal, non-alkali metals and non-alkaline earth metals (e.g., indium (In), germanium (Ge), and bismuth (Bi)), and intermetallic alloys or intermetallic 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, inclusive, preferably in the range of about 10 μm to about 100 μm. According to a variant of the invention, the electrochemically active material of the negative electrode may comprise a film of metallic lithium or an alloy containing metallic lithium.

[0107] According to another example, the positive electrode may be pre-lithiated and the negative electrode may be substantially or completely free of lithium initially (i.e., prior to cycling of the electrochemical cell). The negative electrode may be lithiated in situ during cycling of said electrochemical cell, particularly during the first charge. According to an example, metallic lithium may be disposed on a current collector (e.g., a copper current collector) in situ during cycling of the electrochemical cell, particularly 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, particularly during the first charge. It is understood that the negative electrode may be generated in situ during cycling of the electrochemical cell, particularly during the first charge.

[0108] According to another variation of the object, both the positive electrode and the negative electrode are as defined herein.

[0109] According to another example, the electrolyte may be selected for its compatibility with the different elements of the electrochemical cell. Any type of compatible electrolyte is contemplated. According to one example, the electrolyte is a liquid electrolyte comprising a salt in a solvent. According to one alternative, the electrolyte is a gel electrolyte comprising a salt in a solvent and optionally a solvating polymer. According to another alternative, the electrolyte is a solid polymer electrolyte comprising a salt in a solvating polymer. According to another alternative, the electrolyte comprises an inorganic solid electrolyte material, for example, the electrolyte may be a ceramic type solid electrolyte. According to another alternative, the electrolyte is a polymer-ceramic hybrid solid electrolyte.

[0110] According to another example, the salt, when present in the electrolyte, may be an ionic salt, such as a lithium salt. Non-limiting examples of lithium salts include lithium hexafluorophosphate (LiPF6), 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 (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium nitrate (LiNO3), lithium chloride. (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiOTf), lithium fluoroalkylphosphate Li[PF3(CF2CF3)3] (LiFAP), lithium tetrakis(trifluoroacetoxy)borate Li[B(OCOCF3)4] (LiTFAB), lithium bis(1,2-benzenediolato(2-)-O,O')borate Li[B(C6O2)2] (LiBBB), lithium difluoro(oxalato)borate (LiBF2(C2O4)) (LiFOB), with the formula LiBF2O4R x (In the formula, R x =C 2~4and combinations of at least two thereof.

[0111] According to another example, the solvent, when 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 (γ-BL) and γ-valerolactone (γ-VL); acyclic ethers, such as 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (D EE), ethoxymethoxyethane (EME), trimethoxymethane, and ethyl monoglyme; cyclic ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, and dioxolane derivatives; and other solvents, such as dimethylsulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, phosphoric acid triesters, sulfolane, methylsulfolane, propylene carbonate derivatives, and mixtures thereof.

[0112] According to another example, the electrolyte is a gel electrolyte or a gel polymer electrolyte. The gel polymer electrolyte may, for example, optionally include 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. Examples of gel electrolytes include, but are not limited to, gel electrolytes such as those described in PCT patent applications published in WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0113] According to another example, the gel electrolyte or liquid electrolyte defined above may also be impregnated into a separator, for example 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 commercially available polymer separator of the Celgard™ type.

[0114] According to 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 different components of the electrochemical cell. The solid polymer electrolyte composition generally includes a salt and one or more solid polar polymers, which are optionally crosslinked. A polyether-type polymer, such as one based on polyethylene oxide (POE), may be used, although 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, such as star polymers or comb polymers, such as those described in PCT patent application published in WO2003 / 063287 (Zaghib et al.).

[0115] According to another example, the solid polymer electrolyte composition may comprise a block copolymer comprised of at least one lithium ion solvating segment and, optionally, at least one crosslinkable segment. Preferably, the lithium ion solvating segment is represented by Formula VIII: [ka] (In the formula, R is a hydrogen atom and C1 to C 10 Alkyl group or -(CH2-OR a R b ) group; Ra is (CH2-CH2-O) y and; R b is a hydrogen atom and C1-C 10 alkyl groups; x is an integer selected from the range of 10 to 200,000; y is an integer selected from the range of 0 to 10. The repeat unit is selected from homopolymers or copolymers having the following repeat units:

[0116] According to another example, a crosslinkable segment of the copolymer is a polymer segment that contains at least one functional group that is crosslinkable in multiple dimensions by irradiation or heat treatment.

[0117] According to another example, the electrolyte comprises an ionically conductive inorganic solid electrolyte material and may comprise ceramic, glass, or glass-ceramic particles, such as fluoride, phosphide, sulfide, oxysulfide, oxide-based ceramic, glass, or glass-ceramic particles, or a combination of at least two thereof. According to a variant of interest, the electrolyte comprises ceramic, glass, or glass-ceramic particles as described above.

[0118] According to another example, the electrolyte is a polymer-ceramic hybrid solid electrolyte, which may for example comprise particles of an inorganic material as defined herein pre-dispersed in a solid polymer electrolyte as defined above. Alternatively, the polymer-ceramic hybrid solid electrolyte comprises a layer of a ceramic electrolyte as defined above between two layers of a solid polymer electrolyte as defined above.

[0119] According to another example, the electrolyte may also contain additives, such as ion-conducting materials as defined above, inorganic particles, glass or ceramic particles, and other additives of the same type, as needed. According to another example, the additive may be a dicarbonyl compound, such as those described in PCT patent application published in WO2018 / 116529 (Asakawa et al.). For example, the additive may be poly(ethylene-alt-maleic anhydride) (PEMA). The additive may be selected from all known electrolyte additives and may be selected for its compatibility with the different elements of the electrochemical cell. According to an example, the additive may be substantially dispersed in the electrolyte. Alternatively, the additive may be present in separate layers.

[0120] According to certain examples, electrode binders comprising the polymer blends defined herein can significantly improve the dispersion of different components, particularly solid components, of a positive electrode material. For example, electrode binders comprising the polymer blends defined herein can significantly promote the dispersion of electrochemically active materials, electronically conductive materials, and / or ceramic-type solid electrolyte materials. For example, the R of the polynorbornene-based polymer of the polymer blend of said binders can be used to significantly improve the dispersion of different components, particularly solid components, of a positive electrode material. 1 and / or R 2 The group may be a group that can promote the dispersion of one of these materials. For example, a carboxyl group (-COOH) may be a group that can promote the dispersion of one of these materials. Without wishing to be bound by theory, for example, repulsive interactions associated with the polymer blend of the materials may allow for better dispersion of the positive electrode components in the dispersion, which may be by modifying or not modifying other components that allow this type of interaction. For example, the repulsive interactions may be of the π-π and / or polar type.

[0121] According to another example, the different components of the positive electrode material can be modified to substantially increase the repulsive interaction with the polymer mixture of said binder and thus promote their dispersion. For example, the different components of the positive electrode can be modified by coating them with a coating material that promotes repulsive interactions, such as π-π and / or polar type interactions. According to an example, at least one of the electrochemically active material, the electronically conductive material, and the ceramic type electrolyte material can be coated with a coating material that promotes repulsive interactions. For example, the coating material may include at least one branched or linear unsaturated aliphatic hydrocarbon having 10 to 50 carbon atoms and having at least one carbon-carbon double or triple bond. 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 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 the variant of interest, the additional component is decane or a mixture containing decane and tetrahydrofuran. Conductive materials, such as carbon, can also be modified by grafting groups, for example, as described in the PCT patent application published under 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. Ion and electronic conduction phenomena can be further enhanced, and the electrochemical double layer can present improved stability.

[0122] The present technology also relates to a battery comprising at least one electrochemical cell as defined herein. For example, the battery can be a primary battery (cell) or a secondary battery (accumulator). According to an 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 an all-solid-state battery. EXAMPLES

[0123] The following examples are for illustrative purposes and should not be construed as further limiting the scope of the invention as contemplated, and are better understood with reference to the accompanying drawings. Example 1 Preparation of argyrodite-type ceramic particles of formula Li6PS5Cl. a) Coating of Li6PS5Cl particles with a mixture of heptane and dibutyl ether (50:50 by volume)

[0124] The coating of Li6PS5Cl particles was carried out by a wet particle milling process.

[0125] Coating of the Li6PS5Cl particles was performed during wet milling using a PULVERISETTE™ 7 planetary micromill to reduce particle size. The coating material included a mixture of heptane and dibutyl ether (50:50 by volume). 4 g of Li6PS5Cl particles were placed in an 80 mL zirconium oxide (or zirconia) grinding jar. A mixture including 13 mL of heptane and 13 mL of anhydrous dibutyl ether (50:50 by volume) and grinding beads with a diameter of 2 mm were added to the jar. The Li6PS5Cl particles and the mixture of heptane and dibutyl ether were mixed by grinding at a speed of about 300 rpm for about 7.5 hours to produce Li6PS5Cl particles coated with a mixture of heptane and dibutyl ether. The resulting particles were then dried under vacuum at a temperature of about 80°C. b) Coating of Li6PS5Cl particles with a mixture of decane and squalene (75:25 by volume).

[0126] The coating of Li6PS5Cl particles was carried out by wet milling and mechanosynthesis process.

[0127] The coating of Li6PS5Cl particles was carried out using a PULVERISETTE™ 7 planetary micromill. 4 g of Li6PS5Cl particles were placed in an 80 ml zirconium oxide grinding jar. A mixture containing 20 ml of anhydrous decane and 7 ml of squalene (75:25 by volume), and grinding beads with a diameter of 2 mm were added to the jar. The Li6PS5Cl particles and the mixture of decane and squalene were mixed by grinding at a speed of about 300 rpm for about 7.5 hours to produce Li6PS5Cl particles coated with the mixture of decane and squalene. The resulting particles were then dried under vacuum at a temperature of about 80°C. c) Coating of Li6PS5Cl particles with a mixture of decane and squalene (90:10 by volume)

[0128] The coating of Li6PS5Cl particles was carried out by wet milling and mechanosynthesis process.

[0129] The coating of Li6PS5Cl particles was carried out using a PULVERISETTE™ 7 planetary micromill. 4 g of Li6PS5Cl particles were placed in an 80 ml zirconium oxide grinding jar. A mixture of decane and squalene (90:10 by volume) and grinding beads with a diameter of 2 mm were added to the jar. The Li6PS5Cl particles and the mixture of decane and squalene were mixed by grinding at a speed of about 300 rpm for about 7.5 hours to produce Li6PS5Cl particles coated with the mixture of decane and squalene. The resulting particles were then dried under vacuum at a temperature of about 80° C. Example 2 Preparation of modified electronically conductive materials a) grafting particles of an electronically conductive material with at least one aryl group of formula VII

[0130] The following process for the production of electronically conductive material was applied to carbon black.

[0131] 5 g of carbon black was dispersed in 200 ml of 0.5 M aqueous sulfuric acid (H2SO4), then 0.01 equivalents of aniline p-substituted with a hydrophilic substituent (-SO3H, which was then lithiated to exchange the hydrogen with lithium) was added to the mixture (i.e., 0.01 equivalents of aniline relative to carbon black). The mixture was then vigorously stirred until the amine was completely dissolved.

[0132] After addition of 0.03 equivalents of sodium nitrite (NaNO2) relative to the carbon black (e.g., 3 equivalents of NaNO2 relative to the aniline), the corresponding aryl diazonium ion was generated in situ and reacted with the carbon black. The mixture thus obtained was allowed to react overnight at room temperature.

[0133] Once the reaction was complete, the mixture was filtered under vacuum using a vacuum filtration assembly (Buchner 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 electronically conductive particles with a mixture of decane and squalene (75:25 by volume)

[0134] The coating of particles of electronically conductive material is carried out by wet particle milling and mechanosynthesis processes.

[0135] The coating of carbon black particles is carried out using a PULVERISETTE™ 7 planetary micromill. 4 g of carbon black particles are placed in an 80 ml zirconium oxide grinding jar. A mixture of anhydrous decane and squalene (75:25 by volume) and grinding beads with a diameter of 2 mm are added to the jar. The carbon black particles and the mixture of decane and squalene are mixed by milling 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 resulting particles are then dried under vacuum at a temperature of about 80° C. Example 3 Preparation of positive electrode film

[0136] The composition of the positive electrode film is given in Table 2. [Table 2] * NBR: acrylonitrile-butadiene rubber; SBS: styrene-butadiene-styrene; PB: polybutadiene; PNB: polynorbornene of formula II(b). a) Preparation of the positive electrode film (film 1)

[0137] 1.55 g of LiNi coated with LiNbO3 from a commercial source, with an average diameter of about 4 μm0.6 Mn 0.2 Co 0.2 O2 (NMC 622) particles were mixed with 0.40 g of coated Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0138] A polymer solution was prepared separately by dissolving 0.05 g of acrylonitrile-butadiene rubber (NBR) in 1.187 g of p-xylene. The polymer solution was added to the dry powder mixture. The mixture thus obtained was mixed for about 5 minutes using a planetary centrifugal mixer (Thinky Mixer). An additional amount of solvent (p-xylene) was added to the mixture to achieve an optimal viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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. b) Preparation of the positive electrode film (film 2)

[0139] 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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0140] 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 mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional solvent, methoxybenzene, was added to the mixture to achieve an optimal viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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 the positive electrode film (film 3)

[0141] 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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0142] 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 mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional amount of methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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 the positive electrode film (film 4)

[0143] 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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0144] 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 mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An amount of methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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. e) Preparation of the positive electrode film (film 5)

[0145] 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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0146] 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 mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional amount of the solvent methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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 the positive electrode film (film 6)

[0147] 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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0148] 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 mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional amount of methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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 the positive electrode film (film 7)

[0149] 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 Li6PS5Cl 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 powder was 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 mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional amount of the solvent methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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 the positive electrode film (film 8)

[0151] 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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0152] A polymer solution was prepared separately by dissolving 0.035 g of polybutadiene and 0.015 g of polynorbornene in 0.94 g of THF. The polymer solution was added to the dry powder mixture. The mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional amount of the solvent methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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. i) Preparation of positive electrode film (film 9)

[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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0154] A polymer solution was prepared separately by dissolving 0.030 g of polybutadiene and 0.020 g of polynorbornene in 0.94 g of THF. The polymer solution was added to the dry powder mixture. The mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional amount of the solvent methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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 positive electrode film (film 10)

[0155] 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 Li6PS5Cl 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 powder was mixed for about 10 minutes using a vortex mixer.

[0156] A polymer solution was prepared separately by dissolving 0.025 g of polybutadiene and 0.025 g of polynorbornene in 0.94 g of THF. The polymer solution was added to the dry powder mixture. The mixture thus obtained was mixed for about 5 minutes using a planetary mixer. An additional amount of the solvent methoxybenzene was added to the mixture to achieve the optimum viscosity for coating, i.e., about 10000 cP. The suspension thus obtained was coated on an aluminum foil using 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)-3(j)

[0157] Morphological studies of the different cathode films were carried out using a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectroscopy (EDS) detector.

[0158] 1 shows in (A) an SEM image of the positive electrode film (Film 1) prepared in Example 3(a) and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of the elements Ni and S. The scale bars represent 300 μm and 100 μm, respectively.

[0159] In Fig. 1(A) it is possible to observe the presence of waves on the surface of film 1 after a step of drying this cathode film. Fig. 1(B) confirms the presence of nickel (green) in the electrochemically active material of the cathode (LiNbO3-NMC 622) and sulfur (red) in the solid electrolyte (coated Li6PS5Cl). Fig. 1 also shows 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 disperse the solid electrolyte particles.

[0160] 2 shows in (A) an SEM image of the positive electrode film (film 2) prepared in Example 3(b) and in (B) the corresponding mapping image allowing the analysis of the distribution of the elements Ni and S. The scale bar represents 100 μm.

[0161] In FIG. 2(A) it is possible to observe the absence of waves on the surface of film 2 after a step of drying this cathode film. FIG. 2(B) confirms the presence of nickel (green) and sulfur (red). FIG. 2 also highlights the absence of sulfide aggregates on the surface of film 2. This shows that the use of a solution comprising a blend (80:20 by weight) of polybutadiene and polynorbornene (with -COOH groups) dissolved in THF in the suspension adequately disperses the solid electrolyte particles.

[0162] 3 shows in (A) an SEM image of the positive electrode film (Film 3) prepared in Example 3(c) and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of the elements Ni and S. The scale bar represents 100 μm.

[0163] In FIG. 3(A) it is possible to observe the presence of slight waves on the surface of film 3 after a step of drying this cathode film. FIG. 3(B) confirms the presence of nickel (green) and sulfur (red). FIG. 3 also highlights the presence of sulfide aggregates on the surface of film 3. This indicates that the use of a solution of SBS in methoxybenzene in the suspension does not adequately disperse the solid electrolyte particles.

[0164] 4 shows in (A) an SEM image of the positive electrode film (Film 4) prepared in Example 3(d) and in (B) the corresponding EDS mapping image allowing analysis of the distribution of the elements Ni and S. The scale bar represents 100 μm.

[0165] In FIG. 4(A) it is possible to observe the presence of slight waves on the surface of film 4 after a step of drying this cathode film. FIG. 4(B) confirms the presence of nickel (green) and sulfur (red). FIG. 4 also highlights the presence of sulfide aggregates on the surface of film 4. This indicates that the use of a solution of polybutadiene in THF in the suspension does not adequately disperse the particles of solid electrolyte in the electrode material.

[0166] 5 shows in (A) an SEM image of the positive electrode film (Film 5) prepared in Example 3(e) and in (B) the corresponding EDS mapping image allowing the analysis of the distribution of the elements Ni and S. The scale bar represents 100 μm.

[0167] In FIG. 5(A) it is possible to observe the absence of waves at the surface of the film 5 after a step of drying this cathode film. FIG. 5(B) confirms the presence of nickel (green) and sulfur (red). FIG. 5 also highlights the absence of sulfide aggregates at the surface of the film 5. This shows that the use of a solution containing a blend (80:20 by weight) of polybutadiene and polynorbornene (with -COOH groups) dissolved in THF in the suspension adequately disperses the solid electrolyte particles. Without wishing to be bound by theory, this may be related to the effect of the use of polynorbornene modified with -COOH groups. The dispersion appears to be substantially favored by this type of group and by the carbon bridges linked to the polynorbornene structure itself. The coverage of the sulfide particles by molecules with double or triple bonds appears to substantially improve the dispersion via π-π interactions and / or polar repulsion.

[0168] 6-8 show in (A) SEM images of the positive electrode films (films 7-9) prepared in Examples 3(g)-3(i), respectively, and in (B) top-view SEM images of the same films. Scale bars represent 100 μm.

[0169] Figures 6-8 show good dispersion of the components in these positive electrode films, indicating that the use of a solution containing a blend of polybutadiene and polynorbornene (with -COOH groups) dissolved in THF adequately disperses the coated Li6PS5Cl particles and electronic conductive material due to π-π interactions and polar repulsion. Example 5 Electrochemical properties

[0170] The electrochemical properties of the positive electrode films prepared in Examples 3(a)-3(j) were investigated. a) Electrochemical cell configuration

[0171] The electrochemical cell was assembled according to the following procedure.

[0172] Pellets with a diameter of 10 mm were taken from the cathode films prepared in Examples 3(a)-3(j). A ceramic-type inorganic solid electrolyte based on Li6PS5Cl sulfide was prepared by placing 80 mg of ceramic on the surface of the cathode film. The cathode film pellets with 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 a CR2032 type button battery case facing a metallic lithium electrode with a diameter of 10 mm on a copper current collector. The electrochemical cell was assembled according to the configuration presented in Table 3. [Table 3] b) Behavior of the positive electrode film

[0173] This example illustrates the electrochemical behavior of the electrochemical cell described in Example 5(a).

[0174] The electrochemical cell assembled in Example 5(a) was charged to a Li / Li + The cells were cycled from 4.3 V to 2.5 V vs. C. Cells 1-5 were cycled at a temperature of 50° C. and cells 6-10 were cycled at a temperature of 30° C. The formation cycle was performed at a constant charge and discharge current of C / 15. Then, 4 cycles were performed at a constant charge and discharge current of C / 10, followed by 4 cycles at a constant charge and discharge current of C / 5. Finally, a long-term cycling experiment was performed at a constant charge and discharge current of C / 3.

[0175] 9 shows a graph of discharge capacity (mAh / g) and coulombic efficiency (%) as a function of cycle number for Cell 1 (squares) and Cell 2 (triangles). It can be observed that there is no substantial difference in capacity retention for Cell 1 and Cell 2. In fact, the curves are substantially superimposed for cycling at 50° C. for Cell 1 and Cell 2.

[0176] FIG. 10 shows a graph of the average charge and discharge potential (V) as a function of the number of cycles for cell 1 (squares) and cell 2 (triangles). It is possible to observe that cell 2, which comprises a blend (80:20 by weight) of polybutadiene and polynorbornene (with -COOH groups) as binder, makes it possible to obtain a lower polarization during long-term cycling experiments at a temperature of 50° C. and at constant charge and discharge currents of C / 3. It is also possible to observe a good discharge stability with the blend (80:20 by weight) of polybutadiene and polynorbornene (with -COOH groups). This polymer blend thus ensures a good dispersion of the components of the electrode and, therefore, a good ionic and electronic transmission of said components, without substantially affecting the charge transfer.

[0177] FIG. 11 shows graphs of discharge capacity and coulombic efficiency as a function of cycle number for cell 3 (squares), cell 4 (circles), and cell 5 (triangles). It can be observed that the capacity retention at a temperature of 50° C. and C / 3 is improved when polybutadiene is used in combination with styrene or polynorbornene as the binder. Indeed, cells 3 and 5, which contain a copolymer of styrene and butadiene (styrene-butadiene-styrene (SBS)), and a blend of polybutadiene and polynorbornene, respectively, exhibit improved capacity retention compared to cell 4, which contains polybutadiene.

[0178] Figure 12 shows a graph of the average charge and discharge potential as a function of cycle number for cell 3 (squares), cell 4 (circles) and cell 5 (triangles) (in conjunction with Figure 11). It is possible to observe that cell 3 and cell 5 make it possible to obtain improved polarization during long-term cycling experiments, compared to cell 4. To this may be contributed the adhesion effect provided by styrene or polynorbornene, thus confirming the positive and dispersive effect associated with the use of polynorbornene. Its complementarity with the more elastic polymer thus ensures adhesion during cycling while allowing air permeability of the system.

[0179] FIG. 13 shows graphs of the discharge capacity and coulombic efficiency as a function of cycle number for cell 6 (squares), cell 7 (triangles), cell 8 (circles), cell 9 (inverted triangles), and cell 10 (stars), as well as (A) graphs of the average charge and discharge potentials as a function of cycle number.

[0180] FIG. 14 shows graphs of average charge and discharge potentials as a function of cycle number, related to FIG. 13, for cell 6 (squares), cell 7 (triangles), cell 8 (circles), cell 9 (inverted triangles), and cell 10 (stars).

[0181] Capacity retention upon cycling at C / 3 and 30° C. is slightly affected by the formulation change in that there is a polymer (styrene or polynorbornene) that can provide an adhesive effect.

[0182] Lower polarization can be observed for the positive electrode film (film 9) containing a blend of polybutadiene and polynorbornene (60:40 by weight) as binder, especially on charging. This can be attributed to the dispersing effect of polynorbornene through its -COOH groups and carbon bridges, combined with the repulsion and π-π interactions of the carbon modified with polar groups, and the coverage of the sulfide particles with organic species with double or triple bonds. The adhesion provided by the increased polynorbornene to polybutadiene ratio ensures stability during cycling, while the polybutadiene absorbs the volumetric fluctuations of the active material during cycling while maintaining the particles and contact between these particles.

[0183] Several modifications may be made to any of the above described embodiments without departing from the contemplated scope of the invention. All references, patent or scientific literature referred to in this application are incorporated herein by reference in their entirety for all purposes.

Claims

1. Polybutadiene polymers and formula I: 【Chemistry 14】 [In the formula, R １ and R ２ In their respective appearances, they are: hydrogen atom, carboxyl group (-COOH), sulfonic acid group (-SO). ３ A binder composition comprising a blend containing a polynorbornene polymer containing norbornene monomer units derived from the polymerization of compounds [H], hydroxyl groups (-OH), fluorine atoms, and chlorine atoms (selected from hydroxyl groups (-OH), fluorine atoms, and chlorine atoms).

2. The binder composition according to claim 1, wherein R1 and R2 are independently selected from a hydrogen atom and a -COOH group in their respective appearances.

3. The binder composition according to claim 1, wherein R1 is a -COOH group and R2 is a hydrogen atom, or both R1 and R2 are -COOH groups.

4. The aforementioned polynorbornene-based polymer is given by formula II: 【Chemistry 15】 [In the formula, R １ and R ２ This is as defined in claim 1; n is an integer selected such that the mass-average molecular weight of the polymer of formula II is approximately 10,000 g / mol to approximately 100,000 g / mol, including upper and lower limits. The binder composition according to claim 1, wherein the polymer is [the polymer].

5. The binder composition according to claim 1, wherein the polybutadiene polymer is selected from polybutadiene or epoxidized polybutadiene.

6. The epoxidized polybutadiene is of formulas III, IV, and V: 【Chemistry 16】 The binder composition according to claim 5, comprising a repeating unit and two hydroxyl terminal groups.

7. The epoxidized polybutadiene is given by formula VI: 【Chemistry 17】 [In the formula, m is an integer selected such that the mass-average molecular weight of the epoxidized polybutadiene of formula VI is approximately 1000 g / mol to approximately 1500 g / mol, including upper and lower limits, and the mass-average molecular weight of the epoxidized polybutadiene of formula VI is approximately 1300 g / mol. It is; The epoxide equivalent weight, including upper and lower limits, is approximately 100 g / mol to approximately 600 g / mol. The binder composition according to claim 6.

8. The binder composition according to claim 7, wherein the epoxidized polybutadiene of formula VI is Poly bd™ 600E resin having a mass average molecular weight of about 1300 g / mol and an epoxide equivalent weight of about 400 g / mol to about 500 g / mol, including upper and lower limits, or Poly bd™ 605E resin having a mass average molecular weight of about 1300 g / mol and an epoxide equivalent weight of about 260 g / mol to about 330 g / mol, including upper and lower limits.

9. The binder composition according to any one of claims 1 to 8, wherein the weight ratio of polybutadiene polymer to polynorbornene polymer is in the range of about 6:1 to about 2:3, including upper and lower limits.

10. The binder composition according to any one of claims 1 to 8, further comprising at least one solvent.

11. A binder comprising a binder composition as defined in any one of claims 1 to 8, wherein the binder is used in an electrode material.

12. An electrode material comprising an electrochemically active material and a binder as defined in claim 11.

13. - The electrochemically active material is selected from metal oxides, metal sulfides, metal oxysulfides, metal phosphates, metal fluorophosphates, metal oxyfluorophosphates, metal sulfates, metal halides, metal fluorides, sulfur, selenium, and at least two combinations thereof; 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 at least two combinations thereof; the electrochemically active material further comprises alkali metals or alkaline earth metals selected from lithium (Li), sodium (Na), potassium (K), and magnesium (Mg); or - The electrochemically active material is selected from intermetallic compounds, metal oxides, metal nitrides, metal phosphides, metal phosphates, metal halides, metal fluorides, metal sulfides, metal oxysulfides, carbon, silicon (Si), silicon-carbon composites (Si-C), silicon oxide (SiO ｘ ), silicon oxide-carbon composites (SiO ｘ -C), tin (Sn), tin-carbon composites (Sn-C), tin oxide (SnO ｘ ), tin oxide-carbon composites (SnO ｘ -C), and combinations of at least two thereof, The electrode material according to claim 12.

14. The electrochemically active material is in particulate form and further comprises a coating material. The electrode material according to claim 12.

15. The electrode material according to claim 12, further comprising an electronically conductive material.

16. It also contains additives, here (i) The additive is selected from ion-conducting materials, inorganic particles, glass or glass-ceramic particles, ceramic particles, nanoceramics, salts, and at least two combinations thereof; (ii) The additive comprises fluoride, phosphide, sulfide, oxysulfide, or oxide-based ceramic, glass, or glass-ceramic particles; (iii) The additive is selected from crystalline and / or amorphous forms of LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite-type compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and at least two combinations thereof; (iv) The additive is of the formula: - MLZO; - MLTaO; - MLSnO; - MAGP; - MATLAB; - MLTiO; - MZP; - MCZP; - MGPS; - MGPSO; - MSiPS; - MSiPSO; - MSnPS; - MSnPSO; - MPS; - MPSO; - MZPS; - MZPSO; - xM ２ S-yP ２ S ５ ; - xM ２ S-yP ２ S ５ -zMX; - xM ２ S-yP ２ S ５ -zP ２ O ５ ; - xM ２ S-yP ２ S ５ -zP ２ O ５ -wMX; - xM ２ S-yM ２ O-zP ２ S ５ ; - xM ２ S-yM ２ O-zP ２ S ５ -wMX; - xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ ; - xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ -vMX; - xM ２ S-ySiS ２ ; - MPSX; - MPSOX; - MGPSX; - MGPSOX; - MSiPSX; - MSiPSOX; - MSnPSX; - MSnPSOX; - MZPSX; - MZPSOX; - M ３ OX; - M ２ HOX; - M ３ PO ４ ; - M ３ PS ４ ; and - M ａ PO ｂ N ｃ [In the equation, a = 2b + 3c - 5]; [In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and if M includes an alkaline earth metal ion, the number of M is adjusted to achieve electrical neutrality; X is selected from F, Cl, Br, I, or at least two combinations thereof; a, b, c, d, e, and f are non-zero numbers, independently chosen in each equation to achieve electrical neutrality; v, w, x, y, and z are non-zero numbers, independently selected in each formula to obtain a stable compound. Selected from inorganic compounds; (v) The additive is of formula Li ６ PS ５ X [wherein X is Cl, Br, I, or a combination of at least two of them] is selected from inorganic argylodite compounds; or (vi) The additive is Li ６ PS ５ It is Cl. The electrode material according to claim 12.

17. An electrode comprising the electrode material defined in claim 12, wherein the electrode is a freestanding electrode or is located on a current collector.

18. 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 in claim 17.

19. The electrochemical cell according to claim 18, wherein the electrolyte is a liquid electrolyte containing a salt in a solvent, or a gel electrolyte containing a salt in a solvent and optionally in a solvating polymer, or a solid polymer electrolyte containing a salt in a solvating polymer, or a polymer-ceramic hybrid solid electrolyte, or an inorganic solid electrolyte material.

20. (i) The inorganic solid electrolyte material includes fluoride, phosphide, sulfide, oxysulfide, or oxide-based ceramic, glass, or glass-ceramic particles; (ii) The inorganic solid electrolyte material is selected from crystalline and / or amorphous forms of LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite-type compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and at least two combinations thereof; (iii) The inorganic solid electrolyte material is of formula: - MLZO; - MLTaO; - MLSnO; - MAGP; - MATLAB; - MLTiO; - MZP; - MCZP; - MGPS; - MGPSO; - MSiPS; - MSiPSO; - MSnPS; - MSnPSO; - MPS; - MPSO; - MZPS; - MZPSO; - xM ２ S-yP ２ S ５ ; - xM ２ S-yP ２ S ５ -zMX; - xM ２ S-yP ２ S ５ -zP ２ O ５ ; - xM ２ S-yP ２ S ５ -zP ２ O ５ -wMX; - xM ２ S-yM ２ O-zP ２ S ５ ; - xM ２ S-yM ２ O-zP ２ S ５ -wMX; - xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ ; - xM ２ S-yM ２ O-zP ２ S ５ -wP ２ O ５ -vMX; - xM ２ S-ySiS ２ ; - MPSX; - MPSOX; - MGPSX; - MGPSOX; - MSiPSX; - MSiPSOX; - MSnPSX; - MSnPSOX; - MZPSX; - MZPSOX; - M ３ OX; - M ２ HOX; - M ３ PO ４ ; - M ３ PS ４ ; and - M ａ PO ｂ N ｃ [In the equation, a = 2b + 3c - 5]; [In the formula, M is an alkali metal ion, an alkaline earth metal ion, or a combination thereof, and if M includes an alkaline earth metal ion, the number of M is adjusted to achieve electrical neutrality; X is selected from F, Cl, Br, I, or at least two combinations thereof; a, b, c, d, e, and f are non-zero numbers, independently chosen in each equation to achieve electrical neutrality; v, w, x, y, and z are non-zero numbers, independently selected in each formula to obtain a stable compound. Selected from inorganic compounds; (iv) The inorganic solid electrolyte material is of formula Li ６ PS ５ Selected from argyrodite-type inorganic compounds of X [wherein X is Cl, Br, I, or a combination of at least two of them]; or (v) The inorganic solid electrolyte material is Li ６ PS ５ It is Cl. The electrochemical cell according to claim 19.

21. - The negative electrode includes an alkali metal, an alkaline earth metal, an alloy containing at least one alkali metal or alkaline earth metal, an alloy or intermetallic compound, and an electrochemically active material; or - The electrochemical cell according to claim 18, wherein the positive electrode is pre-lithified, the negative electrode is substantially lithium-free, and the negative electrode is lithified in situ during the cycling of the electrochemical cell.

22. An electrochemical battery comprising at least one electrochemical cell as defined in claim 18, wherein the electrochemical battery 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.

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