Electrode binders comprising a blend of polybutadiene polymers and polynorbornene polymers, electrodes containing the same, and their use in electrochemistry.

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 Canadian Provisional Patent Application No. 3,120,992, filed on 3 June 2021, under applicable law, the contents of which are incorporated herein by reference in their entirety for all purposes.

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

[0003] background The development of polymer and / or ceramic 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 consists 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 these together 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. In fact, solid elements can tend to aggregate during the mixing step with the binder, which can lead to non-uniformity of the electrode material. Among the strategies used to solve this problem, the inventors have found that encapsulating the particles of the different components of the system with a coating material improves their dispersion. These dispersion problems can also be significantly reduced by using binders, additives, or dispersion media that improve particle dispersion.

[0006] Norbornene-based polymers are described as additives in the PCT patent application published as WO2020 / 061710 (Daigle et al.), and these are added to polymer binders. Polynorbornene is added to suppress 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] The Korean patent published in KR10-2193945 and the PCT patent application published in WO2019 / 004714 describe a method for producing a solid electrolyte film containing a sulfide-based solid electrolyte, as well as a composite electrode film that enables improved dispersion, density, and ionic conductivity between solid electrolyte particles and between solid electrolyte particles and active material particles by crystallization from amorphous to crystalline state. Norbornene copolymers, particularly poly(ethylene-co-propylene-co-5-methylene-2-norbornene (PEPMNB)), are used to accomplish this. 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 Specification [Patent Document 2] International Publication No. 2019 / 004714 [Overview of the Initiative] [Means for solving the problem]

[0009] overview According to one embodiment, this technology involves a polybutadiene-based polymer and formula I:

Chem.

[0010] In one embodiment, the polynorbornene-based polymer is of Formula II:

Chem.

[0011] In another embodiment, the weight average molecular weight of the polymer of Formula II is from about 12000 g / mol to about 85000 g / mol, or from about 15000 g / mol to about 75000 g / mol, or from about 20000 g / mol to about 65000 g / mol, or from about 25000 g / mol to about 55000 g / mol, or from about 25000 g / mol to about 50000 g / mol, inclusive of the upper and lower bounds.

[0012] In another embodiment, R 1 and R 2 are, independently at each occurrence, selected from a hydrogen atom and a -COOH group. According to one example, R 1 is a -COOH group, and R 2 is a hydrogen atom. According to another example, R 1 and R 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 polybutadiene. According to one example, the epoxidized polybutadiene has the formulae III, IV and V:

Chemical Formula

[0015] According to another example, the epoxidized polybutadiene has formula VI:

Chemical Formula

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

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

[0018] In another embodiment, the weight ratio of polybutadiene-based polymer: polynorbornene-based polymer is in the range of from about 6:1 to about 2:3, inclusive of the upper limit and the lower limit. For example, the weight ratio is in the range of from about 5.5:1 to about 2:3, or from about 5:1 to about 2:3, or from about 4.5:1 to about 2:3, or from about 4:1 to about 2:3, or from about 6:1 to about 1:1, or from about 5.5:1 to about 1:1, or from about 5:1 to about 1:1, or from about 4.5:1 to about 1:1, or from about 4:1 to about 1:1, inclusive of the upper limit and the lower limit. According to a desired variation, the weight ratio is in the range of from about 4:1 to about 1:1, inclusive of the upper limit and the lower limit.

[0019] According to another aspect, the present technology relates to a binder comprising the binder composition as defined herein. According to one 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 the binder as defined herein.

[0021] In one embodiment, the electrochemically active material is selected from the group consisting of 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 of the foregoing. For example, the metal of the electrochemically active material is selected from the group consisting of 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 of the foregoing. According to one example, the electrochemically active material further comprises an alkali metal or alkaline earth metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and magnesium (Mg).

[0022] In one embodiment, the electrochemically active material is non-alkali Ma or non-alkaline earth ofMetals, 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 dioxide (SiO₂) x ), silicon dioxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and at least two combinations thereof are selected.

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

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

[0025] In another embodiment, the electrode material further includes an electronically conductive material. For example, the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fibers, carbon nanofibers, carbon nanotubes, and at least two combinations thereof. According to a particular example, the surface of the electronically conductive material is given 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 in the range of 1 to 3, preferably n is 1 or 2, or more preferably n is 1. It is grafted with at least one aryl group.

[0026] According to one example, a 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 additives. For example, the additives are 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 one example, the additives include ceramic, glass, or glass-ceramic particles of the fluoride, phosphide, sulfide, oxysulfide, or oxide system. According to another example, the additives are selected from LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite-type compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and combinations of at least two thereof, in crystalline and / or amorphous forms. According to another example, the additive is 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(for example, M7La3Ta2O 12 M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO(for example, M7La3Sn2O 12 );MAGP(for example, M 1+a Al a Ge 2-a (PO4)3);MATP(for example, M 1+a Al a Ti 2-a (PO4)3);MLTiO(for example, M3a La (2 / 3-a) TiO3); MZP (for example, M a Zr b (PO4) c ); MCZP (for example, M a Ca b Zr c (PO4) d ); MGPS (for example, M 10 GeP2S 12 such as M a Ge b P c S d ); MGPSO (for example, M a Ge b P c S d O e ); MSiPS (for example, M 10 SiP2S 12 such as M a Si b P c S d ); MSiPSO (for example, M a Si b P c S d O e ); MSnPS (for example, M 10 SnP2S 12 such as M a Sn b P c S d ); MSnPSO (for example, M a Sn b P c S d O e ); MPS (for example, M7P3S 11 such as M a P b S c ); MPSO (for example, M a P b S c O d ); MZPS (for example, M a Zn b P c S d ); MZPSO (for example, M a Zn b P c S d Oe );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 models such as 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(for example, M a Si b P c S d X e );MSiPSOX(for example, M a Si b P c S d O e X f );MSnPSX (for example, M a Sn b P c S d X e );MSnPSOX(for example, M a Sn b P c S d O e X f );MZPSX(for example, M a Zn b P c S d X e);MZPSOX(for example, M a Zn b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c (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, and are independently selected in each formula to obtain a stable compound. It is selected from inorganic compounds.

[0028] According to the desired modification, the additive is selected from inorganic argyrodite compounds of the formula Li6PS5X (wherein X is Cl, Br, I, or a combination of at least two of them). For example, the additive is Li6PS5Cl.

[0029] In another embodiment, the technology relates to an electrode comprising an electrode material defined herein on a current collector. In another embodiment, the technology relates to a self-supporting electrode comprising an electrode material defined herein.

[0030] In another embodiment, the present invention relates to an electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein at least one of the positive electrode or the negative electrode is as defined herein or comprises an electrode material as defined herein.

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

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

[0033] In another embodiment, the electrolyte is a solid polymer electrolyte containing a salt in a solvated 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 one example, the inorganic solid electrolyte material comprises ceramic, glass, or glass-ceramic particles of the fluoride, phosphide, sulfide, oxysulfide, or oxide system. According to another example, the inorganic solid electrolyte material is selected from LISICON, thio-LISICON, argyrodite, garnet, NASICON, perovskite-type compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and combinations of at least two of them, in crystalline and / or amorphous forms. According to another example, the inorganic solid electrolyte material is 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(for example, M7La3Ta2O 12 M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO(for example, M7La3Sn2O 12 );MAGP(for example, M 1+a Al a Ge 2-a(PO4)3);MATP(for example, M 1+a Al a Ti 2-a (PO4)3);MLTiO(for example, M 3a La (2 / 3-a) TiO3); MZP (for example, M a Zr b (PO4) c );MCZP(for example, M a Ca b Zr c (PO4) d );MGPS(for example, M 10 GeP2S 12 M a Ge b P c S d );MGPSO(for example, M a Ge b P c S d O e );MSiPS(for example, M 10 SiP2S 12 M a Si b P c S d );MSiPSO(for example, M a Si b P c S d O e );MSnPS(for example, M 10 SnP2S 12 M a Sn b P c S d );MSnPSO(for example, M a Sn b P c S d O e );MPS (for example, M7P3S 11 M a P b S c );MPSO (for example, M a P b S c O d );MZPS(for example, M a Zn b P c Sd );MZPSO(for example, M a Zn 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 models such as 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(for example, M a Si b P c S d X e );MSiPSOX(for example, M a Si b P c S d O e X f );MSnPSX (for example, M a Sn b P c S d X e );MSnPSOX(for example, M a Sn b P c S d O e X f );MZPSX(for example, Ma Zn b P c S d X e ); MZPSOX (for example, M a Zn b P c S d O e X f ); M3OX; M2HOX; M3PO4; M3PS4; and M a PO b N c (wherein a=2b+3c-5); (wherein 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 is adjusted to achieve electrical neutrality; 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, independently selected in each formula to achieve electrical neutrality; v, w, x, y and z are non-zero numbers, independently selected in each formula to obtain a stable compound) is selected from the inorganic compounds of

[0036] According to a desired variation, the inorganic solid electrolyte material is selected from argyrodite-type inorganic compounds of formula Li6PS5X, wherein 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 storage battery is a battery selected from lithium batteries, lithium ion batteries, sodium batteries, sodium ion batteries, magnesium batteries, and magnesium ion batteries.

[0039] In another embodiment, the electrochemical battery is an all-solid-state battery. [Brief explanation of the drawing]

[0040] [Figure 1] Figure 1 shows (A) an SEM image of film 1 and (B) a corresponding EDS mapping image that allows for analysis of the distribution of elements Ni and S, as described in Example 4. The scale bars represent 300 μm and 100 μm, respectively.

[0041] [Figure 2] Figure 2 shows the SEM image of film 2 in (A) and the corresponding EDS mapping image in (B) that allows for the analysis of the distribution of elements Ni and S, as described in Example 4. The scale bar represents 100 μm.

[0042] [Figure 3] Figure 3 shows the SEM image of film 3 in (A) and the corresponding EDS mapping image in (B) that allows for analysis of the distribution of elements Ni and S, as described in Example 4. The scale bar represents 100 μm.

[0043] [Figure 4] Figure 4 shows the SEM image of film 4 in (A) and the corresponding EDS mapping image in (B) that allows for analysis of the distribution of elements Ni and S, as described in Example 4. The scale bar represents 100 μm.

[0044] [Figure 5] Figure 5 shows the SEM image of film 5 in (A) and the corresponding EDS mapping image in (B) that allows for analysis of the distribution of elements Ni and S, as described in Example 4. The scale bar represents 100 μm.

[0045] [Figure 6]Figure 6 shows SEM images of film 7 in (A), which allows observation of different layers of the film, and in (B), an SEM image of the top surface of the same film, as described in Example 4. The scale bar represents 100 μm.

[0046] [Figure 7] Figure 7 shows SEM images of film 8, as described in Example 4, in (A) allowing observation of different layers of the film, and in (B) an SEM image of the top surface of the same film. The scale bar represents 100 μm.

[0047] [Figure 8] Figure 8 shows SEM images of film 9, as described in Example 4, in (A) allowing observation of different layers of the film, and in (B) an SEM image of the top surface of the same film. The scale bar represents 100 μm.

[0048] [Figure 9] Figure 9 shows graphs of discharge capacity (mAh / g) and Coulomb efficiency (%) as a function of cycle number for cell 1 (square) and cell 2 (triangle) described in Example 5(b).

[0049] [Figure 10] Figure 10 shows graphs of the average charge and discharge potential (V) as a function of the number of cycles for cell 1 (square) and cell 2 (triangle) as described in Example 5(b).

[0050] [Figure 11] Figure 11 shows graphs of discharge capacity (mAh / g) and Coulomb efficiency (%) as a function of cycle number for cell 3 (square), cell 4 (circular), and cell 5 (triangular) as described in Example 5(b).

[0051] [Figure 12]Figure 12 shows graphs of the average charge and discharge potential (V) as a function of the number of cycles for cell 3 (square), cell 4 (circular), and cell 5 (triangular) as described in Example 5(b).

[0052] [Figure 13] Figure 13 shows graphs of discharge capacity and Coulomb efficiency (%) as a function of cycle number for cells 6 (square), 7 (triangle), 8 (circle), 9 (inverted triangle), and 10 (star) described in Example 5(b).

[0053] [Figure 14] Figure 14 shows graphs of the average charge and discharge potential (V) as a function of the number of cycles for cells 6 (square), 7 (triangle), 8 (circle), 9 (inverted triangle), and 10 (star) described in Example 5(b). [Modes for carrying out the invention]

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

[0055] When the term "approximately" is used herein, it means roughly, within a range, or roughly. For example, when the term "approximately" is used in relation to a number, it means to change the number up or down by only 10% from its nominal value. This term may also take into account, for example, experimental errors or rounding of the device being measured.

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

[0057] Where the article “a” is used to introduce an element in this application, it means “one or more” rather than “sole.” Naturally, where this description states that a particular step, component, element, or characteristic “may” or “can” be included, that particular step, component, element, or characteristic does not have to be included in each embodiment.

[0058] For clarity, the expression "monomer units derived from" and equivalent expressions, as used herein, refer to repeating polymer units obtained from the polymerization of polymerizable monomers.

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

[0060] As used herein, the term "hydrophilic functional group" 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-exclusive examples of hydrophilic functional groups include hydroxyl, carboxyl, sulfonic acid, phosphoric acid, amine, amide, and other similar groups. This expression further encompasses salts of these groups where applicable.

[0061] As used herein, the term "self-supporting electrode" refers to an electrode without a metal current collector.

[0062] Chemical structures described herein are drawn in accordance with the conventions of the art. Furthermore, if an atom, such as a carbon atom, appears to have an incomplete valence, the valence is considered to be filled by one or more hydrogen atoms, even if hydrogen atoms are not explicitly depicted.

[0063] This technology relates to an electrode binder containing a polymer blend, more specifically, to an electrode binder containing a polymer blend for use in all-solid-state electrochemical systems.

[0064] More specifically, this technology uses a polybutadiene-based polymer and formula I: [ka] (In the formula, R 1 and R 2 (Each of these atoms is independently selected from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom, and a chlorine atom.) The present invention relates to an electrode binder comprising a blend containing a polynorbornene polymer containing norbornene monomer units derived from the polymerization of a compound.

[0065] According to one example, R 1 or R 2 At least one of these is selected from -COOH, -SO3H, -OH, -F, and -Cl, and this is R 1 or R 2 This means that at least one of them is different from a hydrogen atom.

[0066] In another example, R 1 It is a -COOH group, and R 2 This is a hydrogen atom.

[0067] In another example, R 1 or R 2At least one of them is a -COOH group, and the norbornene monomer unit is a carboxylic acid-functionalized norbornene monomer unit. According to the desired modification, R 1 It is a -COOH group, R 2 is a hydrogen atom. According to another variation of the objective, R 1 and R 2 Both are -COOH groups. This technology involves a polybutadiene polymer and formula II: [ka] (In the formula, R 1 and R 2 (As defined above, 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, as determined by gel permeation chromatography (GPC).) The invention also relates to electrode binders, including blends containing polynorbornene-based polymers.

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

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

[0070] In another example, polynorbornene polymers are given by formula II(a): [ka] (In the formula, R 2(and n are as defined above) It is a polymer. In another example, polynorbornene polymers are given by formula II(b): [ka] (In the formula, n is as defined above.) It is a polymer.

[0071] In another example, the polynorbornene polymers of formula II, II(a), or II(b) are homopolymers.

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

[0073] For example, polynorbornene polymers produced by addition polymerization processes can be substantially stable under harsh conditions (e.g., acidic and basic conditions). Addition polymerization of polynorbornene polymers can be carried out using inexpensive norbornene monomers. The glass transition temperature (T) obtained by the polynorbornene polymers produced by this polymerization pathway is... g The temperature is approximately equal to or higher than 300°C, for example, it may be around 350°C.

[0074] In another example, polybutadiene polymers exhibit substantially higher elasticity or flexibility and / or substantially lower glass transition temperatures (T) than polynorbornene polymers of formula II, II(a), or II(b). g ) can be characterized by:

[0075] In another example, the polybutadiene polymer may be polybutadiene. Alternatively, the polybutadiene polymer may be a functionalized polybutadiene or a polybutadiene-derived polymer. For example, compared to unfunctionalized polybutadiene, functionalized polybutadiene or a polybutadiene-derived polymer has substantially higher elasticity or flexibility and / or substantially lower glass transition temperature (T g ) may be characterized by, and / or the mechanical properties or adhesiveness of the electrode binder may be improved.

[0076] In another example, the polybutadiene polymer is selected from epoxidized polybutadienes, for example, epoxidized polybutadienes having a reactive end group. For example, the reactive end group may be a hydroxyl group. Epoxidized polybutadienes are given by formulas III, IV, and V: [ka] It may also contain repeating units and two hydroxyl terminal groups.

[0077] In another example, the mass-average molecular weight of epoxidized polybutadiene containing repeating units of formulas III, IV, and V may be approximately 1000 g / mol to approximately 1500 g / mol, including upper and lower limits, as determined by GPC.

[0078] In another example, the epoxide equivalent weight of epoxidized polybutadiene containing repeating units of formulas III, IV, and V, as determined by GPC, is approximately 100 g / mol to approximately 600 g / mol, including upper and lower limits. The epoxide equivalent weight corresponds to the mass of resin containing 1 mole of epoxide functional groups.

[0079] According to the intended modification, epoxidized polybutadiene is given by formula VI: [ka] (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, as determined by GPC. It is, The epoxide equivalent weight is determined by GPC and ranges from approximately 100 g / mol to approximately 600 g / mol, including upper and lower limits.

[0080] According to another example, the mass-average molecular weight of epoxidized polybutadiene containing repeating units of formulas III, IV, and V, or epoxidized polybutadiene of formula VI, as determined by GPC, including upper and lower limits, is approximately 1050 g / mol to approximately 1450 g / mol, or approximately 1100 g / mol to approximately 1400 g / mol, or approximately 1150 g / mol to approximately 1350 g / mol, or approximately 1200 g / mol to approximately 1350 g / mol, or approximately 1250 g / mol to approximately 1350 g / mol. According to the variation of the choice, the mass-average molecular weight of epoxidized polybutadiene containing repeating units of formulas III, IV, and V, or epoxidized polybutadiene of formula VI, as determined by GPC, is approximately 1300 g / mol.

[0081] According to another example, the epoxide equivalent weight of epoxides of epoxides containing repeating units of formulas III, IV, and V, or epoxides of formula VI, as determined by GPC, including upper and lower limits, is approximately 150 g / mol to approximately 550 g / mol, or approximately 200 g / mol to approximately 550 g / mol, or approximately 210 g / mol to approximately 550 g / mol, or approximately 260 g / mol to approximately 500 g / mol. According to the variation of the choice, the epoxide equivalent weight of epoxides of epoxides containing repeating units of formulas III, IV, and V, or epoxides of formula VI, as determined by GPC, including upper and lower limits, is approximately 400 g / mol to approximately 500 g / mol, or approximately 260 g / mol to approximately 330 g / mol.

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

[0083] It is understood that the electrode binder comprises a polymer blend comprising at least one first polymer and at least one second polymer. The first polymer is a polybutadiene polymer, and the second polymer is a polynorbornene polymer containing norbornene 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 in the range of approximately 6:1 to approximately 2:3, including upper and lower limits. For example, the "first polymer:second polymer" ratio is in the range of approximately 5.5:1 to approximately 2:3, or approximately 5:1 to approximately 2:3, or approximately 4.5:1 to approximately 2:3, or approximately 4:1 to approximately 2:3, or approximately 6:1 to approximately 1:1, or approximately 5.5:1 to approximately 1:1, or approximately 5:1 to approximately 1:1, or approximately 4.5:1 to approximately 1:1, or approximately 4:1 to approximately 1:1. According to the variation of the object in question, the "first polymer:second polymer" ratio is in the range of approximately 4:1 to approximately 1:1, including upper and lower limits.

[0085] In 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 the polymer blend and mix with them efficiently. 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 at least two miscible combinations thereof. According to the desired modification, the solvent is THF, a mixture containing THF and methoxybenzene, a mixture containing toluene and THF, a mixture containing toluene and DEC, a mixture containing toluene and DMAC, a mixture containing p-xylene and THF, a mixture containing m-xylene and THF, a mixture containing o-xylene and THF, a mixture containing p-xylene and DEC, a mixture containing m-xylene and DEC, a mixture containing o-xylene and DEC, or a mixture containing toluene and methoxybenzene. However, the solvent is preferably removed from the electrode where the binder is found before being assembled with the other elements of the electrochemical cell.

[0086] This technology also relates to the use of electrode binders as defined herein in electrode materials. In fact, electrode materials comprising electrode materials containing electrochemically active materials and electrode binders as defined herein are also conceivable.

[0087] According to one example, the electrode materials as defined herein further include electronically conductive materials. Non-limiting examples of electronically conductive materials include carbon sources, e.g., 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 of these.

[0088] In another example, the electronically conductive material, when present in the electrode material, may be a modified electronically conductive material, such as those described in the PCT patent application published in WO2019 / 218067 (Delaporte et al.). For example, a modified electronically conductive material is given 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 in the range of 1 to 3, preferably 1 or 2, or more preferably 1. It may be grafted with at least one aryl group.

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

[0090] According to the desired variation, the electronically conductive material is carbon black optionally grafted with at least one aryl group of formula VII. According to another desired variation, the electronically conductive material may be a mixture comprising at least one modified electronically conductive material. For example, a mixture of carbon black grafted with at least one aryl group of formula VII and carbon fibers (e.g., vapor-grown carbon fibers (VGCF)), carbon nanofibers, carbon nanotubes (CNTs), or a combination of at least two of these.

[0091] In 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 at least two combinations thereof. In yet 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 where applicable. The electrochemically active material may further contain alkali metals or alkaline earth metals, such as lithium (Li), sodium (Na), potassium (K), or magnesium (Mg), as needed.

[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 a combination thereof), LiV3O8, V2O5, LiMn2O4, LiM''O2 (wherein M'' is Mn, Co, Ni, or a combination thereof), Li(NiM''')O2 (wherein M''' is Mn, Co, Al, Fe, Cr, Ti, or Zr, or a combination thereof), and, where applicable, combinations thereof.

[0093] In a specific example, the electrochemically active material is the oxide or phosphate described above.

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

[0095] In another example, the electrode material is the negative electrode material, and the electrochemically active material is non-alkali. and Non-alkaline earth of Metals (e.g., indium (In), germanium (Ge), and bismuth (Bi)), intermetallic compounds (e.g., SnSb, TiSnSb, Cu2Sb, 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 dioxide (SiO₂) x ), silicon dioxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and any combination thereof, if applicable, are selected. For example, metal oxides are given by formula M'''' b O cCompounds of (wherein 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 (wherein 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 (etc.) or lithium molybdenum oxide (Li2Mo4O 13 Compounds such as the following may be selected.

[0096] In another example, electrochemically active materials may be doped with small amounts of other inclusion elements as needed to, for example, adjust or optimize their electrochemical properties. Electrochemically active materials may also be doped by partial substitution of metals with other ions. For example, electrochemically active materials may be doped with transition metals (e.g., Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, or Y) and / or non-transition metals (e.g., Mg, Al, or Sb).

[0097] In another example, the electrochemically active material may be in the form of particles (e.g., microparticles and / or nanoparticles) that may be newly formed or derived from commercial sources. For example, the electrochemically active material may be in the form of particles coated with a layer of coating material having a core-shell structure. The coating material may be an electronically conductive material, for example, a conductive carbon coating. The conductive carbon layer may also be grafted with at least one aryl group of formula VII, if necessary. Alternatively, the coating material may be capable of substantially reducing interfacial reactions at the interface between the electrochemically active material and an electrolyte, for example, a solid electrolyte, particularly a sulfide-based ceramic solid electrolyte (e.g., Li6PS5Cl system). For example, the coating material may be Li2SiO3, Li4Ti5O 12LiTaO3, LiAlO2, Li2O-ZrO2, LiNbO3, combinations thereof where appropriate, and other similar materials may be selected. Depending on the desired modification, the coating material may contain LiNbO3.

[0098] In another example, the electrode material as defined herein further comprises additives. For example, the additives are 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 thereof. For example, the additives may be ion conductors selected from crystalline and / or amorphous forms of LISICON, thio-LISICON, argyrodites, garnets, NASICON, perovskite compounds, oxides, sulfides, sulfur halides, phosphates, thiophosphates, and combinations of at least two thereof.

[0099] Depending on the intended modification, the additive may be ceramic, glass, or glass-ceramic particles in crystalline and / or amorphous forms when present in the electrode material. For example, the ceramic, glass, or glass-ceramic particles may be fluorides, phosphides, sulfides, oxysulfides, oxide systems, or a combination of at least two of these. 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(for example, M7La3Ta2O 12 M5La3Ta2O 12, and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO(for example, M7La3Sn2O 12 );MAGP(for example, M 1+a Al a Ge 2-a (PO4)3);MATP(for example, M 1+a Al a Ti 2-a (PO4)3);MLTiO(for example, M 3a La (2 / 3-a) TiO3); MZP (for example, M a Zr b (PO4) c );MCZP(for example, M a Ca b Zr c (PO4) d );MGPS(for example, M 10 GeP2S 12 M a Ge b P c S d );MGPSO(for example, M a Ge b P c S d O e );MSiPS(for example, M 10 SiP2S 12 M a Si b P c S d );MSiPSO(for example, M a Si b P c S d O e );MSnPS(for example, M 10 SnP2S 12 M a Sn b P c S d );MSnPSO(for example, M a Sn b P c S d O e );MPS (for example, M7P3S 11 M a Pb S c );MPSO (for example, M a P b S c O d );MZPS(for example, M a Zn b P c S d );MZPSO(for example, M a Zn b 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 models such as 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(for example, M a Si b P c S d X e );MSiPSOX(for example, M a Si b P c S d O e X f );MSnPSX (for example, M a Sn b Pc S d X e );MSnPSOX(for example, M a Sn b P c S d O e X f );MZPSX(for example, M a Zn b P c S d X e );MZPSOX(for example, M a Zn b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c (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, and are independently selected in each formula to obtain a stable compound. Examples of inorganic compounds include the following.

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

[0101] For example, if the additive is present in the electrode material, it may be sulfide-based ceramic particles, such as argyrodite-type ceramic particles of the formula Li6PS5X (wherein X is Cl, Br, I, or a combination of at least two of them). According to the desired variation, the additive is argyrodite Li6PS5Cl.

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

[0103] This technology also relates to electrodes comprising electrode materials as defined herein. In one example, the electrode may be on a current collector (e.g., aluminum foil or copper foil). Alternatively, the electrode may be a freestanding electrode.

[0104] This 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 the intended modification, the anode is as defined herein. For example, the electrochemical anode material may be selected for its electrochemical compatibility with the different elements of the electrochemical cell as defined herein. For example, the electrochemically active material of the anode material may have a substantially lower redox potential than that of the electrochemically active material of the cathode.

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

[0107] In another example, the positive electrode may be pre-lithified, and the negative electrode may not initially contain substantially or completely lithium (i.e., before the electrochemical cell is cycled). The negative electrode may be lithified in situ during the electrochemical cell's cycling, particularly during the first charge. In one example, metallic lithium may be placed in situ on the current collector (e.g., a copper current collector) during the electrochemical cell's cycling, particularly during the first charge. In another example, an alloy containing metallic lithium may be generated on the surface of the current collector (e.g., an aluminum current collector) during the electrochemical cell's cycling, particularly during the first charge. It is understood that the negative electrode may be generated in situ during the electrochemical cell's cycling, particularly during the first charge.

[0108] According to another variation of the objective, both the positive and negative electrodes 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 intended. According to one example, the electrolyte is a liquid electrolyte containing a salt in a solvent. According to another alternative, the electrolyte is a gel electrolyte containing a salt in a solvent and optionally in a solvating polymer. According to yet another alternative, the electrolyte is a solid polymer electrolyte containing a salt in a solvating polymer. According to yet another alternative, the electrolyte comprises an inorganic solid electrolyte material, for example, the electrolyte may be a ceramic solid electrolyte. According to yet another alternative, the electrolyte is a polymer-ceramic hybrid solid electrolyte.

[0110] In another example, when present in an electrolyte, the salt 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), and lithium chloride. (LiCl), lithium bromide (LiBr), lithium fluoride (LiF), lithium perchlorate (LiClO4), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiSO3CF3) (LiOTf), lithium fluoroalkyl phosphate 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), formula LiBF2O4R x (In the formula, R x =C 2~4 Examples include salts of alkyl groups and at least two combinations thereof.

[0111] In another example, the solvent may be a non-aqueous solvent if it is present in the electrolyte. Non-limiting examples of solvents include cyclic carbonates, e.g., ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC); acyclic carbonates, e.g., dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and dipropyl carbonate (DPC); lactones, e.g., γ-butyrolactone (γ-BL) and γ-valerolactone (γ-VL); acyclic ethers, e.g., 1,2-dimethoxyethane (DME), 1,2-diethoxyethane (D Examples include EE), ethoxymethoxyethane (EME), trimethoxymethane, and ethyl monoglycerides; cyclic ethers, such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, and dioxolane derivatives; and other solvents, such as dimethyl sulfoxide, formamide, acetamide, dimethylformamide, acetonitrile, propylnitrile, nitromethane, triesters of phosphate, sulfolane, methylsulfolane, propylene carbonate derivatives, and mixtures thereof.

[0112] In another example, the electrolyte is a gel electrolyte or a gel polymer electrolyte. A gel polymer electrolyte may, for example, optionally contain a polymer precursor and salt (e.g., the salts defined above), a solvent (e.g., the solvents defined above), and a polymerization and / or crosslinking initiator. Examples of gel electrolytes include, but are not limited to, those described in the PCT patent applications published in WO2009 / 111860 (Zaghib et al.) and WO2004 / 068610 (Zaghib et al.).

[0113] In another example, the gel electrolyte or liquid electrolyte defined above may also be impregnated with a separator, such as a polymer separator. Examples of separators, but not limited to, include 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] In another example, the electrolyte is a solid polymer electrolyte. For example, the solid polymer electrolyte composition may be selected from any known solid polymer electrolyte composition, or it may be selected for its compatibility with the different components of the electrochemical cell. The solid polymer electrolyte composition generally comprises a salt and one or more solid polar polymers, which are crosslinked as needed. Polyether-type polymers, such as polyethylene oxide (POE)-based ones, may be used, but several other compatible polymers are also known and intended for the preparation of solid polymer electrolytes. The polymers may be crosslinked. Examples of such polymers include branched polymers, such as star-shaped polymers or comb-shaped polymers, as described in the PCT patent application published in WO2003 / 063287 (Zaghib et al.).

[0115] In another example, the solid polymer electrolyte composition may include a block copolymer comprising a segment that solvates at least one lithium ion, and optionally at least one crosslinkable segment. Preferably, the lithium ion solvating segment is of formula VIII: [ka] (In the formula, R is a hydrogen atom, and C1~C 10 Alkyl or -(CH2-OR a R b ) Selected from the base; Ra (CH2-CH2-O) y and; R b This includes hydrogen atoms and C1~C 10 Selected from alkyl groups; x is an integer selected from the range of 10 to 200,000; (y is an integer selected from the range 0 to 10.) Selected from homopolymers or copolymers having repeating units.

[0116] In another example, a crosslinkable segment of a copolymer is a polymer segment containing at least one functional group that can be crosslinked in multiple dimensions by irradiation or heat treatment.

[0117] In another example, the electrolyte comprises an ion-conductive inorganic solid electrolyte material and may include ceramic, glass, or glass-ceramic particles. For example, fluoride, phosphide, sulfide, oxysulfide, oxide-based ceramic, glass, or glass-ceramic particles, or a combination of at least two thereof. According to the desired variation, the electrolyte comprises the ceramic, glass, or glass-ceramic particles described above.

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

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

[0120] According to one example, an electrode binder containing a polymer blend as defined herein can significantly improve the dispersion of different components of the cathode material, particularly solid components. For example, an electrode binder containing a polymer blend as defined herein can significantly promote the dispersion of electrochemically active materials, electronically conductive materials, and / or ceramic solid electrolyte materials. For example, the polynorbornene-based polymer of the polymer blend of the binder 1 and / or R 2 The group may be one that can promote the dispersion of one of these materials. For example, a carboxyl group (-COOH) may be one that can promote the dispersion of one of these materials. While we do not wish to be bound by theory, for example, repulsive interactions related to the polymer blend of the materials may allow for better dispersion of the cathode component in the dispersion, which may be achieved by modifying or not modifying other components that enable this type of interaction. For example, the repulsive interactions may be of the π-π and / or polar type.

[0121] In another example, different components of the cathode material can be modified to substantially increase the repulsive interaction with the polymer mixture of the binder and thus to promote their dispersion. For example, different components of the cathode can be modified by coating them with a coating material that promotes repulsive interactions, e.g., π-π and / or polar interactions. In one example, at least one of an electrochemically active material, an electronically conductive material, and a ceramic electrolyte material can be coated with a coating material that promotes repulsive interactions. For example, the coating material may contain at least one branched or linear unsaturated aliphatic hydrocarbon having 10 to 50 carbon atoms and at least one carbon-carbon double or triple bond. For example, such a coating material may be a mixture containing the unsaturated aliphatic hydrocarbon and additional components. The additional components may be an alkane (e.g., an alkane having 10 to 50 carbon atoms), or a mixture containing an alkane (e.g., as defined herein) and a polar solvent (e.g., tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or at least two miscible combinations thereof). Depending on the desired modification, the additional component is decane, or a mixture containing decane and tetrahydrofuran. Conductive materials, such as carbon, can also be modified by grafting groups, as described in the PCT patent application published, for example, WO2019 / 218067. In some examples, the electrochemical properties of the cathode material are not substantially negatively affected by these modifications and their interactions. Ionic and electron conduction phenomena may be further enhanced, and the electrochemical bilayer may exhibit improved stability.

[0122] This technology also relates to batteries comprising at least one type of electrochemical cell as defined herein. For example, the battery may be a primary battery (cell) or a secondary battery (storage battery). In one example, the battery is selected from the group consisting of lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, magnesium batteries, magnesium-ion batteries, potassium batteries, and potassium-ion batteries. According to a variation of the subject, the battery is an all-solid-state battery. [Examples]

[0123] The following embodiments are illustrative and should not be construed as further limiting the scope of the invention as intended. These embodiments will be better understood by referring 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 Li6PS5Cl particles were coated using a wet particle milling process.

[0125] The Li6PS5Cl particles were coated during wet milling using a PULVERISETTE® 7 planetary micromill to reduce particle size. The coating material consisted of 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 containing 13 mL of heptane and 13 mL of anhydrous dibutyl ether (50:50 by volume), as well as grinding beads with a diameter of 2 mm, were added to the jar. The Li6PS5Cl particles, along with the heptane and dibutyl ether mixture, were mixed by grinding at a speed of approximately 300 rpm for approximately 7.5 hours to produce Li6PS5Cl particles coated with the heptane and dibutyl ether mixture. The resulting particles were then dried under vacuum at a temperature of approximately 80°C. b) Coating of Li6PS5Cl particles with a mixture of decane and squalene (75:25 by volume)

[0126] Li6PS5Cl particles were coated using a wet milling and mechanosynthesis process.

[0127] The Li6PS5Cl particles were coated 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), as well as grinding beads with a diameter of 2 mm, were added to the jar. The Li6PS5Cl particles and the decane and squalene mixture were mixed by grinding at a speed of approximately 300 rpm for approximately 7.5 hours to produce Li6PS5Cl particles coated with the decane and squalene mixture. The resulting particles were then dried under vacuum at a temperature of approximately 80°C. c) Coating of Li6PS5Cl particles with a mixture of decane and squalene (90:10 by volume)

[0128] Li6PS5Cl particles were coated using a wet milling and mechanosynthesis process.

[0129] The Li6PS5Cl particles were coated 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), as well as grinding beads with a diameter of 2 mm, were added to the jar. The Li6PS5Cl particles and the decane and squalene mixture were mixed by grinding at a speed of approximately 300 rpm for approximately 7.5 hours to produce Li6PS5Cl particles coated with the decane and squalene mixture. The resulting particles were then dried under vacuum at a temperature of approximately 80°C. (Example 2) Preparation of modified electronically conductive materials a) Grafting of electron-conducting material particles with at least one aryl group of formula VII

[0130] The following processes for creating electronically conductive materials were applied to carbon black.

[0131] 5 g of carbon black was dispersed in 200 ml of 0.5 M aqueous sulfuric acid (H2SO4) solution, and then 0.01 equivalents of aniline p-substituted with a hydrophilic substituent (-SO3H, which was subsequently lithified to exchange hydrogen with lithium) were 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 adding 0.03 equivalents of sodium nitrite (NaNO2) to carbon black (for example, 3 equivalents of NaNO2 relative to aniline), the corresponding aryldiazonium ions were generated in situ and reacted with the carbon black. The resulting mixture was then allowed to react overnight at room temperature.

[0133] After 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 continuously washed with deionized water and then with acetone until a neutral pH was reached. Finally, the modified carbon black powder was dried under vacuum at 100°C for at least one day before use. b) Coating of electron-conducting particles with a mixture of decane and squalene (75:25 by volume)

[0134] The electronically conductive material particles are coated using a wet particle milling and mechanosynthesis process.

[0135] The carbon black particles are coated 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), as well as grinding beads with a diameter of 2 mm, are added to the jar. The carbon black particles and the decane and squalene mixture are mixed by grinding at a speed of approximately 300 rpm for approximately 7.5 hours to produce carbon black particles coated with the decane and squalene mixture. The resulting particles are then dried under vacuum at a temperature of approximately 80°C. (Example 3) Preparation of positive electrode film

[0136] The composition of the positive electrode film is shown 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 commercially available LiNbO3, having an average diameter of approximately 4 μm.0.6 Mn 0.2 Co 0.2 O2(NMC 622) particles were mixed with 0.40 g of coated Li6PS5Cl particles and 0.5 g of carbon black, prepared in Example 1(a), which had an average diameter of approximately 200 nm, to form a dry powder mixture. The dry powder was mixed for approximately 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 resulting mixture was mixed for approximately 5 minutes using a Thinky Mixer. An additional amount of solvent (p-xylene) was added to the mixture to achieve the optimal viscosity for coating, i.e., approximately 10,000 cP. The resulting suspension was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the current collector. The positive electrode film was then dried under vacuum at a temperature of approximately 120°C for approximately 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 approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(a), and 0.5 g of carbon black to form a dry powder mixture. The dry powders were mixed using a vortex mixer for approximately 10 minutes.

[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 rotary-orbit mixer. Methoxybenzene, an additional solvent, was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(b), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. Additional methoxybenzene was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(b), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. A certain amount of methoxybenzene was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(b), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. An additional amount of solvent, methoxybenzene, was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(c), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. Additional methoxybenzene was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(c), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. An additional amount of solvent, methoxybenzene, was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(c), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. An additional amount of solvent, methoxybenzene, was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 the positive electrode film (film 9)

[0153] 1.55 g of LiNbO3-coated NMC 622 particles, having an average diameter of approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(c), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. An additional amount of solvent, methoxybenzene, was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the 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 the positive electrode film (film 10)

[0155] 1.55 g of LiNbO3-coated NMC 622 particles, having an average diameter of approximately 4 μm, were mixed with 0.40 g of coated Li6PS5Cl particles, having an average diameter of approximately 200 nm, prepared in Example 1(c), and 0.5 g of modified carbon black to form a dry powder mixture. The dry powders were mixed for approximately 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 rotary-orbit mixer. An additional amount of solvent, methoxybenzene, was added to the mixture to achieve the optimal viscosity for coating, i.e., about 10,000 cP. The suspension thus obtained was coated onto aluminum foil using the doctor blade coating method to obtain a positive electrode film coated on the current collector. The positive electrode film was then dried under vacuum at a temperature of about 120°C for about 5 hours. (Example 4) Characterization of the positive electrode films prepared in Examples 3(a) to 3(j)

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

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

[0159] In Figure 1(A), the presence of waves on the surface of film 1 can be observed after the drying step of the positive electrode film. Figure 1(B) confirms the presence of nickel (green) in the electrochemically active material of the positive electrode (LiNbO3-NMC 622) and sulfur (red) in the solid electrolyte (coated Li6PS5Cl). Figure 1 also shows the presence of sulfide aggregates 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] Figure 2 shows, in (A), an SEM image of the cathode film (film 2) prepared in Example 3(b), and in (B), a corresponding mapping image that allows for analysis of the distribution of elements Ni and S. The scale bar represents 100 μm.

[0161] In Figure 2(A), the absence of waves on the surface of film 2 can be observed after the drying step of this cathode film. Figure 2(B) confirms the presence of nickel (green) and sulfur (red). Figure 2 also highlights the absence of sulfide aggregates on the surface of film 2. This indicates that the use of a solution containing a blend of polybutadiene and polynorbornene (with -COOH groups) dissolved in THF in a suspension (80:20 by weight) allows for proper dispersion of solid electrolyte particles.

[0162] Figure 3 shows, in (A), an SEM image of the cathode film (film 3) prepared in Example 3(c), and in (B), a corresponding EDS mapping image that allows for analysis of the distribution of elements Ni and S. The scale bar represents 100 μm.

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

[0164] Figure 4 shows, in (A), an SEM image of the cathode film (film 4) prepared in Example 3(d), and in (B), a corresponding EDS mapping image that allows for analysis of the distribution of elements Ni and S. The scale bar represents 100 μm.

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

[0166] Figure 5 shows, in (A), an SEM image of the cathode film (film 5) prepared in Example 3(e), and in (B), a corresponding EDS mapping image that allows for analysis of the distribution of elements Ni and S. The scale bar represents 100 μm.

[0167] In Figure 5(A), it is possible to observe the absence of waves on the surface of film 5 after the drying step of this cathode film. Figure 5(B) confirms the presence of nickel (green) and sulfur (red). Figure 5 also highlights the absence of sulfide aggregates on the surface of film 5. This indicates that the use of a solution containing a blend of polybutadiene and polynorbornene (with -COOH groups) dissolved in THF in a suspension (80:20 by weight) allows for proper dispersion of solid electrolyte particles. While we do not wish to be bound by theory, this may be related to the effect of using polynorbornene modified with -COOH groups. The dispersion appears substantially favorable due to this type of group and the carbon crosslinking linked to the polynorbornene structure itself. Coating of sulfide particles with molecules having double or triple bonds appears to substantially improve dispersion via π-π interactions and / or polar repulsion.

[0168] Figures 6-8 show (A) SEM images of the positive electrode films (films 7-9) prepared in Examples 3(g)-3(i), respectively, and (B) SEM images of the top surface of the same films. The scale bar represents 100 μm.

[0169] Figures 6-8 show the good dispersion of components in these cathode films. This indicates that the use of a solution containing a blend of polybutadiene and polynorbornene (with -COOH groups) dissolved in THF effectively disperses the coated Li6PS5Cl particles and electronically 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) to 3(j) were studied. a) Configuration of an electrochemical cell

[0171] The electrochemical cell was assembled following these steps.

[0172] Pellets with a diameter of 10 mm were taken from the positive electrode films prepared in Examples 3(a) to 3(j). A Li6PS5Cl sulfide-based ceramic inorganic solid electrolyte was prepared by placing 80 mg of ceramic on the surface of the positive electrode film. The positive electrode film pellets with the inorganic solid electrolyte layer were then compressed using a press under a pressure of 2.8 tons. These were then assembled in a glove box in a CR2032 type button cell case facing a 10 mm diameter metallic lithium electrode on a copper current collector. The electrochemical cell was assembled according to the configuration shown in Table 3. [Table 3] b) Behavior of the positive electrode film

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

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

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

[0176] Figure 10 shows graphs of the average charge and discharge potential (V) as a function of the number of cycles for cell 1 (square) and cell 2 (triangle). It can be observed that cell 2, containing a blend of polybutadiene and polynorbornene (with -COOH groups) as a binder (80:20 by weight), allows for lower polarization during long-term cycling experiments at a temperature of 50°C, as well as during constant charge and discharge currents of C / 3. Good discharge stability can also be observed with the blend of polybutadiene and polynorbornene (with -COOH groups) (80:20 by weight). Thus, this polymer blend ensures good dispersion of the electrode components and, therefore, good ion and electron permeability of the components without substantially affecting charge transfer.

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

[0178] Figure 12 shows graphs of the average charge and discharge potential as a function of the number of cycles for cell 3 (square), cell 4 (circular), and cell 5 (triangular) (linked with Figure 11). It is possible to observe that cells 3 and 5, compared to cell 4, are able to obtain improved polarization during long-term cycling experiments. This may be due to the adhesive effect provided by styrene or polynorbornene, and thus positive and dispersive effects associated with the use of polynorbornene are confirmed. Its complementarity with a more elastic polymer thus ensures adhesion during cycling while allowing air permeability of the system.

[0179] Figure 13 shows graphs of discharge capacity and Coulomb efficiency as a function of cycle number for cells 6 (square), 7 (triangle), 8 (circle), 9 (inverted triangle), and 10 (star), as well as graphs of average charge and discharge potential as a function of cycle number in (B).

[0180] Figure 14 shows graphs of the average charge and discharge potential as a function of the number of cycles for cells 6 (square), 7 (triangle), 8 (circle), 9 (inverted triangle), and 10 (star), related to Figure 13.

[0181] The capacity retention rate during cycling at C / 3 and 30°C is slightly affected by changes in the formulation, in that there is a polymer (styrene or polynorbornene) that can provide an adhesive effect.

[0182] Lower polarization can be observed, particularly during charging, for cathode films (film 9) containing a blend of polybutadiene and polynorbornene (60:40 by weight) as a binder. This may be due to the dispersion effect of polynorbornene via its -COOH groups and carbon crosslinking, combined with the repulsion and π-π interactions of carbon modified by polar groups, as well as the coating of sulfide particles by organic species having double or triple bonds. The adhesion provided by the increasing polynorbornene-to-polybutadiene ratio ensures stability during cycling, while polybutadiene absorbs volume fluctuations of the active material during cycling, maintaining contact between particles and these particles.

[0183] Several modifications can be made to any of the embodiments described above without departing from the intended scope of the present invention. References, patents, or scientific documents referenced in this application are incorporated herein by reference in their entirety for all purposes. The present invention provides, for example, the following items: (Item 1) Polybutadiene polymers and formula I: [ka] [In the formula, R 1 and R 2 Each of these atoms is independently selected from a hydrogen atom, a carboxyl group (-COOH), a sulfonic acid group (-SO3H), a hydroxyl group (-OH), a fluorine atom, and a chlorine atom in its respective appearance. A binder composition comprising a blend containing a polynorbornene polymer containing norbornene monomer units derived from the polymerization of a compound. (Item 2) The aforementioned polynorbornene-based polymer is, Formula II: [ka] [In the formula, R 1 and R 2 This is as defined in item 1; n is an integer selected such that the mass-average molecular weight of the polymer in formula II is approximately 10,000 g / mol to approximately 100,000 g / mol, including the upper and lower limits. A binder composition as described in item 1, which is a polymer. (Item 3) The binder composition according to item 2, wherein the mass-average molecular weight of the polymer of formula II is, including upper and lower limits, about 12,000 g / mol to about 85,000 g / mol, or about 15,000 g / mol to about 75,000 g / mol, or about 20,000 g / mol to about 65,000 g / mol, or about 25,000 g / mol to about 55,000 g / mol, or about 25,000 g / mol to about 50,000 g / mol. (Item 4) R 1 and R 2 A binder composition according to any one of items 1 to 3, wherein each appearance is independently selected from a hydrogen atom and a -COOH group. (Item 5) R 1 is a -COOH group, R 2 A binder composition as described in item 4, wherein the atom is a hydrogen atom. (Item 6) R 1 and R 2 However, both are -COOH groups, as described in item 4. (Item 7) The binder composition according to any one of items 1 to 6, wherein the polybutadiene polymer is polybutadiene. (Item 8) The binder composition according to any one of items 1 to 6, wherein the polybutadiene polymer is selected from epoxidized polybutadiene. (Item 9) The epoxidized polybutadiene is derived from formulas III, IV, and V: [ka] The binder composition according to item 8, comprising a repeating unit and two hydroxyl terminal groups. (Item 10) The epoxidized polybutadiene is given by formula VI: [ka] [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. It belongs to; The equivalent weight of epoxides, including upper and lower limits, is approximately 100 g / mol to 600 g / mol. The binder composition described in item 9. (Item 11) The binder composition according to item 10, wherein the mass-average molecular weight of the epoxidized polybutadiene of formula VI is about 1300 g / mol. (Item 12) The binder composition according to item 10 or 11, wherein the equivalent weight of the epoxide is about 210 g / mol to about 550 g / mol, including upper and lower limits. (Item 13) The binder composition according to any one of items 10 to 12, wherein the epoxidized polybutadiene of formula VI is a Poly bd(trademark) 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. (Item 14) The binder composition according to any one of items 10 to 12, wherein the epoxidized polybutadiene of formula VI is a Poly bd(trademark) 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. (Item 15) A binder composition according to any one of items 1 to 14, 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. (Item 16) The binder composition according to item 15, wherein the weight ratio is within the range of approximately 5.5:1 to approximately 2:3, or approximately 5:1 to approximately 2:3, or approximately 4.5:1 to approximately 2:3, or approximately 4.1 to approximately 2:3, or approximately 6:1 to approximately 1:1, or approximately 5.5:1 to approximately 1:1, or approximately 5.1 to approximately 1:1, or approximately 4.5:1 to approximately 1:1, or approximately 4.1 to approximately 1:1, including upper and lower limits. (Item 17) The binder composition according to item 16, wherein the weight ratio is in the range of approximately 4:1 to approximately 1:1, including upper and lower limits. (Item 18) A binder composition according to any one of items 1 to 17, further comprising at least one solvent. (Item 19) The binder composition according to item 18, wherein the solvent is an aprotic solvent. (Item 20) The binder composition according to item 19, wherein the aprotic solvent is selected from the group consisting of dichloromethane (DCM), N,N-dimethylformamide (DMF), diethyl carbonate (DEC), N,N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), dioxolane, dioxane, toluene, benzene, methoxybenzene, benzene derivatives, tetrahydrofuran (THF), and at least two miscible combinations thereof. (Item 21) The binder composition according to item 19 or 20, wherein the aprotic solvent is a mixture containing THF, a mixture containing THF and methoxybenzene, a mixture containing toluene and THF, a mixture containing toluene and DEC, a mixture containing toluene and DMAC, a mixture containing p-xylene and THF, a mixture containing m-xylene and THF, a mixture containing o-xylene and THF, a mixture containing p-xylene and DEC, a mixture containing m-xylene and DEC, a mixture containing o-xylene and DEC, or a mixture containing toluene and methoxybenzene. (Item 22) The binder composition according to any one of items 19 to 21, wherein the aprotic polar solvent is THF, or a mixture comprising THF and methoxybenzene. (Item 23) A binder comprising a binder composition as defined in any one of items 1 through 22. (Item 24) The binder described in item 23, wherein the binder is used in an electrode material. (Item 25) Electrode materials comprising an electrochemically active material and a binder composition as defined in items 1 to 22 or a binder as defined in item 23. (Item 26) The electrode material according to item 25, wherein 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. (Item 27) The electrode material according to item 26, wherein the metal of the electrochemically active material is selected from titanium (Ti), iron (Fe), manganese (Mn), vanadium (V), nickel (Ni), cobalt (Co), aluminum (Al), chromium (Cr), copper (Cu), zirconium (Zr), niobium (Nb), and at least two combinations thereof. (Item 28) The electrode material according to item 26, wherein the electrochemically active material further comprises an alkali metal or alkaline earth metal selected from lithium (Li), sodium (Na), potassium (K), and magnesium (Mg). (Item 29) The electrode material according to any one of items 26 to 28, wherein the electrochemically active material is a lithium metal oxide. (Item 30) The electrode material according to item 29, wherein the lithium metal oxide is a mixed oxide (NMC) of lithium, nickel, manganese, and cobalt. (Item 31) The electrode material according to any one of items 26 to 28, wherein the electrochemically active material is a lithium metal phosphate. (Item 32) The electrode material according to item 31, wherein the lithium metal phosphate is lithium iron phosphate. (Item 33) The electrochemically active material is non-alkali Ma or non-alkaline earth of Metals, 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 dioxide (SiO₂) x ), silicon dioxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and electrode materials according to item 25, selected from at least two combinations thereof. (Item 34) The electrode material according to any one of items 25 to 33, wherein the electrochemically active material further comprises a doping element. (Item 35) The electrode material according to any one of items 25 to 34, wherein the electrochemically active material is in the form of particles. (Item 36) The electrode material according to item 35, wherein the particles of the electrochemically active material further comprise a coating material. (Item 37) The coating material is Li2SiO3, Li4Ti5O 12 Electrode materials as described in item 36, selected from LiTaO3, LiAlO2, Li2O-ZrO2, LiNbO3, other similar materials, and combinations of at least two of them. (Item 38) The electrode material according to item 37, wherein the coating material is LiNbO3. (Item 39) The electrode material according to item 36, wherein the coating material is an electronically conductive material. (Item 40) The electrode material according to item 39, wherein the aforementioned electronically conductive material is carbon. (Item 41) Electrode materials according to any one of items 25 to 40, further comprising electronically conductive materials. (Item 42) The electrode material according to item 41, wherein the electronically conductive material is selected from the group consisting of carbon black, acetylene black, graphite, graphene, carbon fiber, carbon nanofiber, carbon nanotube, and at least two combinations thereof. (Item 43) The electrode material according to item 41 or 42, wherein the electronically conductive material is carbon black. (Item 44) The surface of the aforementioned electronically conductive material is given 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. An electrode material according to any one of items 41 to 43, grafted with at least one aryl group. (Item 45) The electrode material according to item 44, wherein the hydrophilic functional group is a carboxylic acid functional group or a sulfonic acid functional group. (Item 46) The electrode material according to item 45, wherein the aryl group of formula VII is p-benzoic acid or p-benzenesulfonic acid. (Item 47) Electrode material according to any one of items 25 to 46, further comprising additives. (Item 48) The electrode material according to item 47, wherein 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. (Item 49) The electrode material according to item 47 or 48, wherein the additive comprises ceramic, glass, or glass-ceramic particles of a fluoride, phosphide, sulfide, oxysulfide, or oxide system. (Item 50) The electrode material according to any one of items 47 to 49, wherein 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 combinations of at least two thereof. (Item 51) The aforementioned additive is given by formula: - MLZO (for example, 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 (for example, M7La3Ta2O) 12 M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 ); - MLSnO (e.g., M7La3Sn2O) 12 ); - MAGP (for example, M 1+a Al a Ge 2-a (PO4)3); - MATP (for example, M 1+a Al a Ti 2-a (PO4)3); - MLTiO (for example, M 3a La (2 / 3-a) TiO3); - MZP (for example, M a Zr b (PO4) c ); - MCZP (for example, M a Ca b Zr c (PO4) d ); - MGPS (for example, M 10 GeP2S 12 M a Ge b P c S d ); - MGPSO (for example, M a Ge b P c S d O e ); - MSiPS (for example, M 10 SiP2S 12 M a Si b P c S d ); - MSiPSO (for example, M a Si b P c S d O e ); - MSnPS (for example, M 10 SnP2S 12 M a Sn b P c S d ); - MSnPSO (for example, M a Sn b P c S d O e ); - MPS (for example, M7P3S) 11 M a P b S c ); - MPSO (for example, M a P b S c O d ); - MZPS (for example, M a Zn b P c S d ); - MZPSO (for example, M a Zn b 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) 11M models such as 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 (for example, M a Si b P c S d X e ); - MSiPSOX (for example, M a Si b P c S d O e X f ); - MSnPSX (for example, M a Sn b P c S d X e ); - MSnPSOX (for example, M a Sn b P c S d O e X f ); - MZPSX (for example, M a Zn b P c S d X e ); - MZPSOX (for example, M a Zn b P c S d Oe X f ); - M3OX; - M2HOX; - M3PO4; - M3PS4; 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. An electrode material selected from inorganic compounds, as described in any one of items 47 to 50. (Item 52) The electrode material according to item 51, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and at least two combinations thereof. (Item 53) Electrode material as described in item 52, where M is Li. (Item 54) The electrode material according to any one of items 47 to 53, wherein the additive is selected from inorganic argyrodite-type compounds of the formula Li6PS5X [wherein X is Cl, Br, I, or a combination of at least two thereof]. (Item 55) The electrode material according to any one of items 47 to 54, wherein the additive is Li6PS5Cl. (Item 56) An electrode comprising an electrode material defined in any one of items 25 to 55 on a current collector. (Item 57) A self-supporting electrode comprising an electrode material as defined in any one of items 25 to 55. (Item 58) 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 item 56 or 57, or comprises an electrode material as defined in any one of items 25 to 55. (Item 59) The electrochemical cell according to item 58, wherein the electrolyte is a liquid electrolyte containing a salt in the solvent. (Item 60) The electrochemical cell according to item 58, wherein the electrolyte is a gel electrolyte containing a salt in a solvent and optionally in a solvating polymer. (Item 61) The electrochemical cell according to item 58, wherein the electrolyte is a solid polymer electrolyte containing a salt in a solvated polymer. (Item 62) The electrochemical cell according to item 58, wherein the electrolyte is a polymer-ceramic hybrid solid electrolyte. (Item 63) The electrochemical cell according to item 58, wherein the electrolyte comprises an inorganic solid electrolyte material. (Item 64) The electrochemical cell according to item 63, wherein the inorganic solid electrolyte material comprises ceramic, glass, or glass-ceramic particles of a fluoride, phosphide, sulfide, oxysulfide, or oxide system. (Item 65) The electrochemical cell according to item 63 or 64, wherein the inorganic solid electrolyte material is selected from lithocon, thio-lithocon, argyrodite, garnet, nasicone, perovskite-type compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and combinations of at least two thereof, in crystalline and / or amorphous forms. (Item 66) The inorganic solid electrolyte material is given by formula: - MLZO (for example, M7La3Zr2O) 12 M (7-a) La3Zr2Al b O 12M (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 (for example, M7La3Ta2O) 12 M5La3Ta2O 12 , and M6La3Ta 1.5 Y 0.5 O 12 ); - MLSnO (e.g., M7La3Sn2O) 12 ); - MAGP (for example, M 1+a Al a Ge 2-a (PO4)3); - MATP (for example, M 1+a Al a Ti 2-a (PO4)3); - MLTiO (for example, M 3a La (2 / 3-a) TiO3); - MZP (for example, M a Zr b (PO4) c ); - MCZP (for example, M a Ca b Zr c (PO4) d ); - MGPS (for example, M 10 GeP2S 12 M a Ge b P c S d ); - MGPSO (for example, M a Ge b P c S d O e ); - MSiPS (for example, M 10 SiP2S 12 Ma Si b P c S d ); - MSiPSO (for example, M a Si b P c S d O e ); - MSnPS (for example, M 10 SnP2S 12 M a Sn b P c S d ); - MSnPSO (for example, M a Sn b P c S d O e ); - MPS (for example, M7P3S) 11 M a P b S c ); - MPSO (for example, M a P b S c O d ); - MZPS (for example, M a Zn b P c S d ); - MZPSO (for example, M a Zn b 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 models such as 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 (for example, M a Si b P c S d X e ); - MSiPSOX (for example, M a Si b P c S d O e X f ); - MSnPSX (for example, M a Sn b P c S d X e ); - MSnPSOX (for example, M a Sn b P c S d O e X f ); - MZPSX (for example, M a Zn b P c S d X e ); - MZPSOX (for example, M a Zn b P c S d O e X f ); - M3OX; - M2HOX; - M3PO4; - M3PS4; and - M a PO b N c [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. An electrochemical cell as described in any one of items 63 to 65, selected from the inorganic compounds. (Item 67) An electrochemical cell as described in item 66, wherein M is selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, and at least two combinations thereof. (Item 68) An electrochemical cell as described in item 67, where M is Li. (Item 69) The electrochemical cell according to any one of items 63 to 68, wherein the inorganic solid electrolyte material is selected from argyrodite-type inorganic compounds of the formula Li6PS5X [wherein X is Cl, Br, I, or a combination of at least two thereof]. (Item 70) The electrochemical cell according to any one of items 63 to 69, wherein the inorganic solid electrolyte material is Li6PS5Cl. (Item 71) The negative electrode is an alkali metal, an alkaline earth metal, or at least one alkali metal or alkaline earth metal. alloys containing , non-alkaline and Non-alkaline earth of metal 、 An electrochemical cell according to any one of items 58 to 70, comprising an electrochemically active material including an alloy or intermetallic compound. (Item 72) The electrochemical cell according to item 71, wherein the electrochemically active material of the negative electrode comprises metallic lithium or an alloy containing metallic lithium. (Item 73) The electrochemical cell according to item 71 or 72, wherein the electrochemically active material of the negative electrode is in the form of a film having a thickness in the range of about 5 μm to about 500 μm, including upper and lower limits. (Item 74) The electrochemical cell according to item 73, wherein the thickness of the film of the electrochemically active material of the negative electrode is in the range of about 10 μm to about 100 μm, including upper and lower limits. (Item 75) An electrochemical cell according to any one of items 58 to 70, wherein the positive electrode is pre-lithified and the negative electrode is substantially lithium-free. (Item 76) The electrochemical cell according to any one of item 75, wherein the negative electrode is lithium-ionized in situ during the cycling of the electrochemical cell. (Item 77) An electrochemical battery comprising at least one electrochemical cell as defined in any one of items 58 to 76. (Item 78) The electrochemical battery according to item 77, wherein the electrochemical battery is a battery selected from lithium batteries, lithium-ion batteries, sodium batteries, sodium-ion batteries, magnesium batteries, and magnesium-ion batteries. (Item 79) The electrochemical battery described in item 78, wherein the battery is a lithium battery or a lithium-ion battery. (Item 80) The electrochemical battery described in item 78, wherein the electrochemical battery is an all-solid-state battery.

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 the group consisting of 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 of the foregoing, 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 lithicon, thiolithicon, argyrodite, garnet, nasicon, perovskite-type compounds, oxides, sulfides, oxysulfides, phosphides, fluorides, and at least two combinations thereof, in crystalline and / or amorphous forms; (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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