Polymer-inorganic particle compositions, methods of preparation, and use in electrochemical cells

Abstract

Described herein are compositions comprising polymers and inorganic particles. The polymers in these compositions are the reaction products of at least one monomer comprising at least one polymerizable or crosslinkable functional group and an organic compound comprising one or more SH groups. Methods for preparing the compositions and their use in elements of electrochemical cells are also described. In a preferred embodiment, the compositions are solid. According to another preferred embodiment, the compositions do not comprise a polymerization initiator or a crosslinker.

Description

[Technical field]

[0001] Related Applications This application claims priority under applicable law to Canadian Patent Application No. 3,145,586, filed January 14, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] Technical Field The present technology relates to a composition comprising a polymer and inorganic particles, wherein the polymer is a reaction product of at least one monomer containing at least one polymerizable or crosslinkable functional group and an organic compound containing one or more SH groups. [Background technology]

[0003] background The liquid electrolytes used in lithium-ion batteries are flammable and slowly decompose, forming a passivation layer on the surface of the lithium film or solid electrolyte interface (or solid electrolyte interphase, SEI) where lithium is irreversibly consumed, reducing the coulombic efficiency of the battery. Furthermore, the lithium anode undergoes significant morphological changes during cycling of the battery, leading to the formation of lithium dendrites. As lithium dendrites typically migrate through the electrolyte, they can potentially cause short circuits.

[0004] Safety concerns and the demand for higher energy density have prompted research into the development of all-solid-state lithium rechargeable batteries containing polymer or ceramic (or ceramic-polymer composite) electrolytes, both of which are more stable relative to lithium metal and reduce the growth of lithium dendrites. However, several drawbacks arise from the use of such solid electrolytes, such as loss of reactivity or ionic conductivity, and poor contact between solid interfaces.

[0005] Furthermore, methods of fabricating solid electrolytes containing polymers, either as solid polymer electrolytes or in ceramic-polymer composites, generally require the presence of polymerization initiators and heating or irradiation polymerization conditions, which often require additional equipment and longer fabrication times. Similarly, such polymerization initiators may remain trapped inside the film and interfere with the electrochemical reactions, for example, during cycling.

[0006] Thus, there is a continuing need to develop new electrolyte compositions and methods for their preparation. Summary of the Invention [Means for solving the problem]

[0007] overview According to a first aspect, the present technology relates to a composition comprising a polymer and inorganic particles, wherein the polymer is a reaction product of at least one monomer comprising at least one polymerizable or crosslinkable functional group and an organic compound comprising one or more SH groups.

[0008] According to one embodiment, the monomer has the formula R 2 (X) m is a compound of R 2 is an organic group, X is a polymerizable or crosslinkable group, m is a number in the range of 1 to 8, or the monomer is of the formula R 2 (X) m In some embodiments, the non-crosslinkable polymer segment is present and has a structure represented by Formula I: [ka] It is of (In the formula, R is a hydrogen atom, C1-C 10 Alkyl group or -(CH2-OR a -R b ) group, Ra is (CH2-CH2-O) j or (CH(CH3)-CH2-O) j and R b is a hydrogen atom or C1-C 10 is an alkyl group, i is an integer selected from the range of 2 to 200,000; and j is an integer selected from the range of 0 to 100.

[0009] According to another embodiment, X is a polymerizable or crosslinkable group containing a double bond. According to some embodiments, X is a group of the formula -R 3 -C(R 4 )=CH2 group, and R 3 is O, NH, OCH2, NHCH2, OC(O), NHC(O) or is absent and forms a covalent bond, R 4 H, C1~C 10 Alkyl or C3-C 10 It is cycloalkyl.

[0010] According to one embodiment, the polymer units derived from the monomer have at least one formula: [ka] Includes units of (In the formula, R 2 , R 3 , R 4 and m is as defined above; [ka] is C(R 3 R 4 ) or CH2, represents a bond to a hydrogen atom or a bond to a sulfur atom derived from an organic compound, an end group, or another polymer unit; R 2 represents a macromonomer).

[0011] According to another embodiment, R 2 , or R 2The macromonomers containing linear or branched C 2~12 is selected from alkyl, alkylene oxide or poly(alkylene oxide), alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, and monocyclic or polycyclic aromatic groups, e.g., R 2 is linear or branched C 2~12 It is selected from alkyl, alkylene oxide or poly(alkylene oxide) and phenyl groups.

[0012] In some embodiments, m is a number included in the range of 2-4.

[0013] According to one embodiment, the monomers are selected from branched poly(ethylene glycol)s containing acrylate groups at the ends of the main chain and / or side chains and / or on the chain, poly(ethylene glycol) diacrylate, pentaerythritol tetraacrylate, triethylene glycol divinyl ether, ethylene glycol dimethacrylate and divinylbenzene.

[0014] According to some embodiments, the polymer units derived from the monomer have at least one formula: [ka] Includes units of (In the formula, R 4 and [ka] is as defined above, and p is a number different from zero).

[0015] According to one embodiment, R 4 is H or C1-C6 alkyl, preferably H or C1-C3 alkyl, more preferably H or methyl.

[0016] According to another embodiment, the monomer content in the composition (before reaction) is in the range of about 1% to about 95% by weight, or about 2% to about 90% by weight, or about 3% to about 80% by weight, or about 4% to about 50% by weight, or about 10% to about 70% by weight, or about 20% to about 65% by weight.

[0017] According to some preferred embodiments, the organic compound has the formula R 1 (SH) n R 1 is an organic moiety linking the SH groups and n is a number ranging from 1 to 10, or the compound has the formula R 1 (SH) n It is a macromonomer comprising at least one segment comprising units of

[0018] According to another embodiment, the polymer units derived from an organic compound have at least one formula: [ka] Includes units of (In the formula, R 1 and n is as defined above, [ka] represents a linkage to another polymer unit, such as a unit derived from a monomer, when attached to a sulfur atom, and R 1 represents a macromonomer).

[0019] In one embodiment, R 1 , or R 1 The segment containing is linear or branched C 2~12 Alkyl, linear or branched C 2~12Selected from alkyl polyol ethers or esters, alkylene oxides or poly(alkylene oxides) optionally containing one or more sulfur atoms in the chain, alkylene sulfides or poly(alkylene sulfides), siloxanes or polysiloxanes, mono- or polycycloalkyls or heterocycloalkyls, fused or unfused mono- or polycyclic aromatics or heteroaromatics, optionally containing linking atoms, or combinations thereof.

[0020] According to some embodiments, n is a number ranging from 1-4.

[0021] In one embodiment, the organic compound is selected from 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, 2,2'-(ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate) and 4,4'-thiobisbenzenethiol. For example, the polymer units derived from the organic compound have at least one of the formula: [ka] [ka] Includes units of (In the formula, [ka] is as defined above).

[0022] According to some preferred embodiments, the organic compound content in the composition (before reaction) is in the range of about 0.01% to about 60% by weight, or about 0.05% to about 50% by weight, or about 10% to about 30% by weight, or about 15% to about 40% by weight.

[0023] According to one embodiment, the polymer in the composition is a random, block or alternating polymer.

[0024] According to another embodiment, the inorganic particles comprise inorganic compounds of amorphous, ceramic or glass-ceramic type, for example oxide, sulfide or oxysulfide based, the inorganic compounds being natural or synthetic.

[0025] According to one embodiment, the inorganic particles have the formula MLZO (e.g., M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 and M. (7-a) La3Zr (2-b) Nb b O 12 );MLTaO (e.g., M7La3Ta2O 12 , M5La3Ta2O 12 and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO (e.g., M7La3Sn2O 12 );MAGP(e.g., M 1+a Al a Ge 2-a (PO4)3); MATP (e.g., M 1+a Al a Ti 2-a (PO4)3);MLTiO (e.g., M 3a La (2 / 3-a) TiO3);MZP (e.g., M a Zr b (PO4) c );MCZP (e.g., M a Ca b Zr c (PO4) d );MGPS(e.g., M 10 GeP2S 12 M a Ge b P c S d );MGPSO(e.g., M aGe b P c S d O e ); MSiPS (e.g., M 10 SiP2S 12 M a S b P c S d );MSiPSO (e.g., M a S b P c S d O e ); MSnPS (e.g., M 10 SnP2S 12 M a Sn b P c S d );MSnPSO (e.g., M a Sn b P c S d O e );MPS(e.g., M7P3S 11 M a P b S c );MPSO (e.g., M a P b S c O d );MZPS(e.g., M a Zinc b P c S d );MZPSO(e.g., M a Zinc b P c S d O e );xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5;xM2S- yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example, M7P3S 11 X, M7P2S8X and M6PS5X a P b S c X d);MPSOX(For example, M a P b S c O d X e );MGPSX(M a Ge b P c S d X e );MGPSOX(M a Ge b P c S d O e X f );MSiPSX(M a S b P c S d X e );MSiPSOX(M a S b P c S d O e X f );MSnPSX(M a Sn b P c S d X e );MSnPSOX(M a Sn b P c S d O e X f );MZPSX(M a Zinc b P c S d X e );MZPSOX(M a Zinc b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c Contains natural or synthetic ceramics selected from inorganic compounds of (a=2b+3c-5) (In the formula, M is one of an alkali metal, an alkaline earth metal, or a combination thereof, and when M comprises an alkaline earth metal ion, the number of M is adjusted to achieve electroneutrality; X is selected from F, Cl, Br, I, or combinations thereof; a, b, c, d, e and f are numbers different from zero and are independently selected in each formula to achieve electroneutrality; v, w, x, y and z are numbers different from zero and are independently selected in each formula to provide a stable compound.

[0026] In another embodiment, the inorganic particles are selected from the group consisting of Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 , LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silica), sulfide ceramics (Li6PS5Cl, Li7P3S 11 The ceramics include natural or synthetic ceramics selected from glass-ceramics (such as LIPON), glass-ceramics (such as LIPON), and other ceramics, and combinations thereof.

[0027] In some embodiments, the ceramic has the formula Li 7-b La3Zr2M i b O 12 where b is 0≦b≦1, and M i is Al, Ga, Ta, Fe, or Nb, or is absent, e.g., b is 0, M i is absent. In one embodiment, the ceramic is an aluminosilicate compound. In another embodiment, the ceramic is a sulfide or oxysulfide based ceramic.

[0028] According to one embodiment, the inorganic particles are in the form of particles that are one of spheres, rods, needles, nanotubes, or combinations thereof.

[0029] According to a preferred embodiment, the content of inorganic particles in the composition is in the range of about 5% to about 99% by weight, or about 5% to about 90% by weight, or about 10% to about 80% by weight, or about 15% to about 40% by weight.

[0030] In a preferred embodiment, the composition is solid. According to another preferred embodiment, the composition does not contain a polymerization initiator or a crosslinker.

[0031] According to another aspect, the present technology relates to a method for preparing a composition as defined above, comprising a step of mixing inorganic particles, at least one monomer comprising at least one polymerizable or crosslinkable functional group, and an organic compound comprising one or more SH groups.

[0032] In one embodiment, the mixing step is carried out at a temperature in the range of 15°C to 50°C, or in the range of 20°C to 35°C, or in the range of 20°C to 30°C.

[0033] According to another embodiment, the mixing step is carried out in the presence of oxygen (e.g., in air). According to an alternative embodiment, the mixing step is carried out in an inert atmosphere.

[0034] In a preferred embodiment, the method does not include the addition of a polymerization initiator or a crosslinking agent.

[0035] According to another embodiment, the method further comprises applying the resulting mixture to a support surface. In one embodiment, the support is an inert film, and the method optionally comprises removing the film. In another embodiment, the support is an electrode film. In yet another embodiment, the support is a current collector or an electrolyte film.

[0036] According to yet another aspect, the present technology relates to an electrolyte comprising a composition as defined herein or obtained according to the method. According to a preferred embodiment, the electrolyte is in the form of a solid electrolyte film.

[0037] According to another aspect, the present technology relates to a composition as defined herein or obtained according to the method, and an electrode comprising an electrochemically active material. In one embodiment, the electrode further comprises a current collector. According to another embodiment, the electrochemically active material is LiM'PO4 (wherein M' is Fe, Ni, Mn, Co, or a combination thereof), LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM''O2 (wherein M'' is Mn, Co, Ni, or a combination thereof (NMC, LiMn s Co t Ni u The cathode active material may be an electrochemically active material such as Li(NiM''')O2 (where M''' is Mn, Co, Al, Fe, Cr, Ti, Zr or a combination thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material, or a combination of two or more of these materials, if compatible with each other. In another embodiment, the electrode further comprises a conductive material, a binder, a salt, or a combination of two or more of these.

[0038] According to one aspect, the technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, the electrolyte being as defined above. According to one embodiment, the positive electrode comprises an electrochemically active positive electrode material, optionally on a current collector surface. In another embodiment, the electrochemically active positive electrode material is selected from metal phosphates, lithiated metal phosphates, metal oxides and lithiated metal oxides. In an alternative embodiment, the electrochemically active positive electrode material is selected from LiM'PO4 (wherein M' is Fe, Ni, Mn, Co or a combination thereof), LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM''O2 (wherein M'' is Mn, Co, Ni or a combination thereof (NMC, LiMn s Co t Ni uO2, where s+t+u=1), Li(NiM''')O2 (M''' is Mn, Co, Al, Fe, Cr, Ti, Zr or a combination thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials such as graphite, organic cathode active materials, or combinations of two or more of these materials, if compatible with each other. According to another embodiment, the positive electrode material further comprises a conductive material, a binder, a salt and / or inorganic particles. According to another embodiment, the electrolyte is in direct contact with the positive electrode and / or the negative electrode, preferably with the positive electrode.

[0039] Alternatively, the present technology relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, the positive electrode being as defined herein (and comprising the composition). According to one embodiment, the electrolyte and the positive electrode are as defined above.

[0040] According to one embodiment, the negative electrode comprises an electrochemically active negative electrode material and, optionally, a current collector.

[0041] In another embodiment, the electrochemically active negative electrode material comprises a metal film comprising an alkali metal or alkaline earth metal, or an alloy comprising an alkali metal or alkaline earth metal. According to one embodiment, the alkali metal is selected from lithium and sodium, or an alloy comprising one of these.

[0042] According to another embodiment, the electrochemically active negative electrode material is selected from the group consisting of intermetallic compounds (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxides (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations thereof, where compatible. According to one embodiment, the metal oxide is represented by the formula M"" g O h Examples of suitable oxides include, for example, MoO3, MoO2, MoS2, V2O5, and TiNb2O7, where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof, and g and h are numbers with the h:g ratio ranging from 2 to 3, spinel oxides (for example, NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM''''O, where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof (for example, lithium titanate (Li4Ti5O 12 ) or lithium molybdate (Li2Mo4O 13 In some embodiments, the negative electrode material further comprises a conductive material, a binder, a salt, inorganic particles, or a combination of two or more thereof.

[0043] According to another aspect, the present technology also relates to a battery comprising at least one electrochemical cell as defined herein. According to one embodiment, the battery is selected from a lithium battery, a lithium ion battery, a sodium battery, a sodium ion battery, a potassium battery, a potassium ion battery, a magnesium battery and a magnesium ion battery. According to another embodiment, the battery is a lithium battery. According to yet another embodiment, the battery is a lithium ion battery. [Brief description of the drawings]

[0044] [Figure 1] FIG. 1 shows (a) the 6Li NMR spectra of LLZO and a TBT / LLZO mixture, and (b) the 13C NMR spectra of TBT and a TBT / LLZO mixture.

[0045] [Diagram 2] FIG. 2 shows the results of impedance measurements on electrolytes containing a sulfide ceramic, an ionic plastic salt (sel pastique ionique) and a macromonomer containing 0.5 wt. % UV crosslinker (circles), 2 wt. % TBT (triangles) or 4 wt. % TBT (squares).

[0046] [Diagram 3] FIG. 3 shows the results of impedance measurements on electrolytes containing a sulfide ceramic, an ionic plastic salt, and a macromonomer with 2 wt. % TBT (triangles), a 30:1 O:Li ratio in LiFSI and 2 wt. % TBT (stars), or a 20:1 O:Li ratio in LiFSI and 2 wt. % TBT (inverted triangles). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0047] Detailed Description All technical and scientific terms and expressions used herein have the same meaning as commonly understood by those skilled in the art. Nevertheless, definitions of some of the terms and expressions used are provided below in this specification.

[0048] When the term "about" is used herein, it means approximately, in the region of, and approximately. For example, when the term "about" is used in reference to a numerical value, the term modifies the nominal value above and below by up to 10% variation. The term can also take into account, for example, experimental error inherent in a measuring device, or rounding of values.

[0049] When a range of values ​​is stated in this application, the upper and lower limits of the range are always included in the definition, unless otherwise specified. When a range of values ​​is stated in this application, all intermediate ranges and subranges, as well as individual values ​​that fall within this value range, are included in the definition.

[0050] When the article "a" is used to introduce an element in this application, the article does not have the meaning of "only one," but rather "one or more." Of course, when the specification specifies that a particular step, component, element, or feature "may be included" or "can be included," that particular step, component, element, or feature does not need to be included in every embodiment.

[0051] The chemical structures described herein are drawn in accordance with conventions in the art. Similarly, when an atom, such as a depicted carbon atom, appears to include an incomplete valence, the valence is considered to be satisfied by one or more hydrogen atoms, even if no hydrogen atoms are explicitly shown.

[0052] As used herein, the term "alkyl" refers to an optionally substituted saturated hydrocarbon group having 1 to 20 (unless otherwise indicated) carbon atoms, including linear or branched alkyl groups. Non-limiting examples of alkyl include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl groups and analogs. Similarly, an "alkylene" group refers to an alkyl group positioned between groups, e.g., methylene, ethylene, propylene, butylene, etc.

[0053] The term "cycloalkyl," as used herein, refers to a group containing a 3- to 15-membered saturated or partially unsaturated carbocyclic ring, which may be in the form of a monocyclic or polycyclic system, including spirocarbocyclic, fused carbocyclic or bridged carbocyclic rings, and which may be optionally substituted.

[0054] The term "heterocycloalkyl" as used herein refers to a monocyclic group having 3 to 7 members, or a bicyclic group having 7 to 15 members, which is chemically stable, saturated or partially unsaturated, and has carbon atoms and 1 to 4 heteroatoms selected from oxygen, nitrogen, and sulfur. When a nitrogen atom is used as a ring atom in a heterocycloalkyl, it is understood that the nitrogen may also contain a hydrogen atom or a substituent. A heterocycloalkyl group may be attached to the remainder of the molecule through a ring carbon atom or a ring nitrogen atom.

[0055] As used herein, the term "aromatic" refers to an aromatic group having 4n+2 conjugated π (pi) electrons in a monocyclic group, where n is a number from 1 to 3, or a fused or non-fused bicyclic or tricyclic system having a total of 6 to 15 ring members, in which at least one of the rings in the system is aromatic.

[0056] The term "heteroaromatic" refers to an aromatic group having 4n+2 (n is a number from 1 to 3) conjugated π (pi) electrons, e.g., 5 to 18 ring atoms, preferably 5, 6 or 9 ring atoms, and having, in addition to carbon atoms, 1 to 5 heteroatoms selected from oxygen, nitrogen and sulfur. When a nitrogen atom is used as a ring atom in a heteroaryl, it is understood that the nitrogen may also contain a hydrogen atom or a substituent. A heteroaryl group may be attached to the remainder of the molecule by a ring carbon atom or a ring nitrogen atom.

[0057] The term "monomer," as used, refers to a molecule that can undergo polymerization. Monomers may include macromonomers, i.e., macromolecules that can themselves undergo polymerization.

[0058] "Macromonomer," when used, more specifically refers to a macromolecule that comprises a polymer chain. The polymer chain of the macromonomer may itself comprise a homopolymer or copolymer, and may include branches such as star, comb, etc., branching to form multiple macromonomers.

[0059] The present specification presents a composition, preferably a solid, comprising a polymer and inorganic particles, where the polymer is a reaction product of at least one monomer containing at least one polymerizable or crosslinkable functional group and an organic compound containing one or more SH groups. The combination of the monomer, the SH group of the organic compound and the inorganic molecule allows polymerization and / or crosslinking and solidification to occur without the addition of polymerization initiators or crosslinking agents (e.g., heat or radiation activators).

[0060] Non-limiting examples of monomers include those of formula R 2 (X) m R 2 is an organic group, X is a polymerizable or crosslinkable group, m is a number in the range of 1 to 8, or the monomer is of the formula R 2 (X) mand optionally a non-crosslinkable polymer segment.

[0061] For example, if a non-crosslinkable polymer segment is present, the polymer segment may be represented by Formula I: [ka] It is of (In the formula, R is a hydrogen atom, C1-C 10 Alkyl group or -(CH2-OR a -R b ) group, R a is (CH2-CH2-O) j or (CH(CH3)-CH2-O) j and R b is a hydrogen atom or C1-C 10 is an alkyl group, i is an integer selected from the range of 2 to 200,000; and j is an integer selected from the range of 0 to 100.

[0062] formula R 2 (X) m In the formula, X is, for example, 3 -C(R 4 )=CH2, R 3 is O, NH, OCH2, NHCH2, OC(O), NHC(O) or is absent and forms a covalent bond, R 4 H, C1~C 10 Alkyl or C3-C 10 Cycloalkyl. R 2 , or R 2 The macromonomers containing linear or branched C 2~12 may be selected from alkyl, alkylene oxide or poly(alkylene oxide), alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, and mono- or polyaromatic groups, preferably R 2 is linear or branched C2~12 In some embodiments, m is a number comprised between 2 and 4. In some embodiments, m is a number comprised between 2 and 4.

[0063] For example, the polymer units derived from the monomers have at least one formula: [ka] Includes units of (In the formula, R 2 , R 3 , R 4 and m is as defined above; [ka] is C(R 3 R 4 ) or CH2, represents a bond to a hydrogen atom or a bond to a sulfur atom from an organic compound, an end group, or another unit from a polymer, and R 2 represents a macromonomer).

[0064] Examples of monomers include branched poly(ethylene glycol), poly(ethylene glycol) diacrylate, pentaerythritol tetraacrylate, triethylene glycol divinyl ether, ethylene glycol dimethacrylate, and divinylbenzene, which contain acrylate groups at the end of the main chain and / or at the side chains, and / or on the chain. Other examples include macromonomers consisting of polyether chains and containing crosslinkable groups (such as acrylate or methacrylate), where the polyether chains are optionally branched (hyperbranched).

[0065] For example, the polymer units derived from the monomers have at least one formula: [ka] [ka] Includes units of (In the formula, R 4 and [ka] is as defined in the formula above, and p is a number different from zero).

[0066] According to some examples, R 4 is H or C1-C6 alkyl, for example H or C1-C3 alkyl, or H or methyl. 4 is attached to the carbon adjacent to the carbonyl, R 4 can be a hydrogen atom or a C1-C6 alkyl (such as C1-C3 alkyl or methyl), and R 4 If R is not attached to the carbon adjacent to the carbonyl (e.g., from the polymerization of a vinyl group), 4 can be a hydrogen atom.

[0067] The monomer content in the composition may be in the range of about 1% to about 95% by weight, or about 2% to about 90% by weight, or about 3% to about 80% by weight, or about 4% to about 50% by weight, or about 10% to about 70% by weight, or about 20% to about 65% by weight.

[0068] Organic compounds containing one or more SH groups generally contain an organic group that serves as a carrier group for the SH group. The organic group can be a linear or branched alkyl, alkenyl or alkynyl group, optionally containing heteroatoms (O, N, S, etc.) and / or optionally substituted. The organic group can also be a monocyclic or polycyclic group, optionally containing heteroatoms (O, N, S, etc.) and / or optionally substituted. The organic group may include an oligomeric or polymeric chain. The organic group may also include a combination of the above elements.

[0069] For example, the organic compound may have the formula R 1 (SH) n R 1is an organic group linking the SH groups, and n is a number ranging from 1 to 10 (or 1 to 4), or the compound has the formula R 1 (SH) n In some examples, R 1 , or R 1 The segment containing is linear or branched C 2~12 Alkyl, linear or branched C 2~12 The organic compound may be selected from alkyl polyol ethers or esters, alkylene oxides or poly(alkylene oxides) optionally containing one or more sulfur atoms in the chain, alkylene sulfides or poly(alkylene sulfides), siloxanes or polysiloxanes, mono- or polycycloalkyls or heterocycloalkyls, fused or unfused mono- or polycyclic aromatics or heteroaromatics, optionally containing linking atoms, or combinations thereof. Non-limiting examples of organic compounds include 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, 2,2'-(ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate), and 4,4'-thiobisbenzenethiol.

[0070] According to some examples, the polymer units derived from the organic compound have at least one formula: [ka] Includes units of (In the formula, R 1 and n is as defined above, [ka] represents a linkage to another polymer unit, such as a unit derived from a monomer, when attached to a sulfur atom, and R 1 represents a macromonomer).

[0071] For example, the polymer units derived from the organic compound have at least one formula: [ka] [ka] Includes units of (In the formula, [ka] is as defined for the two previous formulas).

[0072] The organic compound content in the composition is in the range of about 0.01% by weight to about 60% by weight, or about 0.05% by weight to about 50% by weight, or about 10% by weight to about 30% by weight, or about 15% by weight to about 40% by weight.

[0073] The polymers obtained by reaction of the monomers with the organic compounds can be random, block or alternating polymers.

[0074] The inorganic particles can include, for example, oxide, sulfide or oxysulfide based inorganic compounds of amorphous, ceramic or glass-ceramic type, which may be natural or synthetic. Examples of inorganic compounds include those of the formula MLZO (e.g., M7La3Zr2O 12 , M (7-a) La3Zr2Al b O 12 , M (7-a) La3Zr2Ga b O 12 , M (7-a) La3Zr (2-b) Ta b O 12 and M. (7-a) La3Zr (2-b) Nb b O 12 );MLTaO (e.g., M7La3Ta2O 12 , M5La3Ta2O 12 and M6La3Ta 1.5 Y 0.5 O 12 );MLSnO (e.g., M7La3Sn2O12 );MAGP(e.g., M 1+a Al a Ge 2-a (PO4)3); MATP (e.g., M 1+a Al a Ti 2-a (PO4)3);MLTiO (e.g., M 3a La (2 / 3-a) TiO3);MZP (e.g., M a Zr b (PO4) c );MCZP (e.g., M a Ca b Zr c (PO4) d );MGPS(e.g., M 10 GeP2S 12 M a Ge b P c S d );MGPSO(e.g., M a Ge b P c S d O e ); MSiPS (e.g., M 10 SiP2S 12 M a S b P c S d );MSiPSO (e.g., M a S b P c S d O e ); MSnPS (e.g., M 10 SnP2S 12 M a Sn b P c S d );MSnPSO (e.g., M a Sn b P c S d O e );MPS(e.g., M7P3S 11 M a P b S c );MPSO (e.g., M a P b S c Od );MZPS(e.g., M a Zinc b P c S d );MZPSO(e.g., M a Zinc b P c S d O e );xM2S-yP2S5;xM2S-yP2S5-zMX;xM2S-yP2S5-zP2O5;xM2S-yP2S5-zP2O5-wMX;xM2S-yM2O-zP2S5;xM2S- yM2O-zP2S5-wMX;xM2S-yM2O-zP2S5-wP2O5;xM2S-yM2O-zP2S5-wP2O5-vMX;xM2S-ySiS2;MPSX (for example, M7P3S 11 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(M a Ge b P c S d X e );MGPSOX(M a Ge b P c S d O e X f );MSiPSX(M a S b P c S d X e );MSiPSOX(M a S b P c S d O e X f );MSnPSX(M a Sn b P c S d X e );MSnPSOX(M a Sn b P c Sd O e X f );MZPSX(M a Zinc b P c S d X e );MZPSOX(M a Zinc b P c S d O e X f );M3OX;M2HOX;M3PO4;M3PS4;and M a PO b N c Contains natural or synthetic ceramics selected from inorganic compounds of (a=2b+3c-5) (In the formula, M is one of an alkali metal, an alkaline earth metal, or a combination thereof, and when M comprises an alkaline earth metal ion, the number of M is adjusted to achieve electroneutrality; X is selected from F, Cl, Br, I, or combinations thereof; a, b, c, d, e and f are numbers different from zero and are independently selected in each formula to achieve electroneutrality; v, w, x, y and z are numbers different from zero and are independently selected in each formula to provide a stable compound.

[0075] According to another example, the inorganic particles are Al2O3, Mg2B2O5, Na2O·2B2O3, xMgO·yB2O3·zH2O, TiO2, ZrO2, ZnO, Ti2O3, SiO2, Cr2O3, CeO2, B2O3, B2O, SrBi4Ti4O 15 , LLTO, LLZO, LAGP, LATP, Fe2O3, BaTiO3, γ-LiAlO2, molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silica), sulfide ceramics (Li6PS5Cl, Li7P3S 11 The ceramics include natural or synthetic ceramics selected from glass-ceramics (such as LIPON), glass-ceramics (such as LIPON), and other ceramics, and combinations thereof.

[0076] According to one example, the ceramic may be of the formula Li 7-b La3Zr2M i b O 12 where b is 0≦x≦1, and M i is Al, Ga, Ta, Fe, or Nb, or is absent, e.g., b is 0 and M is absent. According to another example, the ceramic is an aluminosilicate compound. According to yet another example, the ceramic is a sulfide or oxysulfide based ceramic.

[0077] The inorganic particles may be of any shape, for example, as particles that are one of spheres, rods, needles, nanotubes, or combinations thereof.

[0078] The content of inorganic particles in the composition is preferably in the range of about 5% by weight to about 99% by weight, or about 5% by weight to about 90% by weight, or about 10% by weight to about 80% by weight, or about 15% by weight to about 40% by weight.

[0079] After reaction of the monomer with the organic compound, the composition is generally solid. The composition also generally does not include a polymerization initiator or a crosslinking agent, and the polymerization and / or crosslinking is carried out in situ, primarily in the presence of inorganic particles.

[0080] The present specification also describes a method for preparing a composition as defined herein, comprising the step of mixing inorganic particles, at least one monomer comprising at least one polymerizable or crosslinkable functional group, and an organic compound comprising one or more SH groups.

[0081] The mixing step can be carried out at a temperature ranging from 15° C. to 50° C., or from 20° C. to 35° C., or from 20° C. to 30° C. The temperature of the reaction mixture can be higher, but the reaction can be carried out at lower temperatures, or generally without heating (room temperature).

[0082] The mixing step can be carried out in the presence of oxygen (e.g., in air) or in an inert atmosphere (e.g., argon, nitrogen). The choice of atmosphere can depend on the sensitivity to air of the elements contained in the composition or on the type of method selected. For example, the process carried out in the assembly line and subsequently in direct or indirect contact with the lithium film (coating of the mixture or application of a solid film) can be carried out in an anhydrous chamber or in an inert atmosphere. The inorganic compounds used in the composition can also be more sensitive to air.

[0083] The method may further include a step of spreading the composition on a support surface before completing its polymerization. The support may be a film that is eventually removed after polymerization and / or curing of the composition. The support may also be a film intended to remain in contact with the composition. For example, if the composition is used to make an electrolyte, the composition may be applied directly to one or the other of the electrodes. Alternatively, if the composition is included in an electrode material, the composition may be applied to another cell element, such as a current collector or an electrolyte film.

[0084] The composition can be used to manufacture an electrolyte film. The present specification therefore also relates to an electrolyte comprising the composition defined herein or obtained according to the present method. Preferably, the electrolyte is in the form of a solid electrolyte film.

[0085] The compositions described herein may also be used to manufacture electrode materials by mixing with an electrochemically active material and optionally applying to a current collector. The electrode material may also optionally include a conductive material, a binder, a salt, or a combination of two or more thereof.

[0086] For example, the electrochemically active material may be LiM'PO4 (wherein M' is Fe, Ni, Mn, Co, or a combination thereof), LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM''O2 (wherein M'' is Mn, Co, Ni, or a combination thereof (NMC, LiMn s Co t Ni u The cathode active material may be an electrochemically active positive electrode material such as Li(NiM''')O2 (where M''' is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material, or a combination of two or more of these materials if compatible with each other.

[0087] The present specification also relates to an electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined herein.

[0088] The positive electrode may then optionally include an electrochemically active positive electrode material on the current collector surface. The electrochemically active positive electrode material may be selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides. Alternatively, the electrochemically active positive electrode material may be selected from those already described. The positive electrode may also optionally include conductive materials, binders, salts, and / or inorganic particles.

[0089] For example, an electrolyte as defined herein, or a composition intended to form said electrolyte, may be deposited directly onto the film surface of the positive or negative electrode during cell formation, and the electrolyte film thus formed is then in direct contact with the positive and / or negative electrodes, preferably with the positive electrode.

[0090] In the alternative, the electrochemical cell comprises a negative electrode, a positive electrode and an electrolyte, wherein the positive electrode is as defined above and comprises the composition, or both the positive electrode and the electrolyte comprise the composition of the present invention.

[0091] The negative electrode of the electrochemical cells described herein generally comprises an electrochemically active negative electrode material and, optionally, a current collector.

[0092] According to a preferred variant, the electrochemically active negative electrode material comprises a metal film comprising one selected from an alkali metal or alkaline earth metal, or an alloy containing an alkali metal or alkaline earth metal, or preferably lithium or sodium, or an alloy containing one of these.

[0093] Thus, metal films can be made of lithium and any of the following metals: alkali metals other than lithium (such as Na, K, Rb and Cs), alkaline earth metals (such as Mg, Ca, Sr and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, It may also be an alloy with an element selected from iron, boron, indium, thallium, nickel and germanium (e.g., Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni or Ge), preferably a lithium alloy containing at least 50%, or at least 75%, or at least 90%, or at least 95%, or at least 99% lithium by weight.

[0094] According to another variation, the electrochemically active negative electrode material is selected from the group consisting of intermetallic compounds (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb2, FeSn2, and CoSn2), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi2(PO4)3), metal halides (e.g., metal fluorides), metal sulfides, metal oxysulfides, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), silicon-carbon composites (Si-C), silicon oxides (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations thereof, where compatible. For example, the metal oxide can be represented by the formula M"" g O h Examples of suitable oxides include, for example, MoO3, MoO2, MoS2, V2O5, and TiNb2O7, where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof, and g and h are numbers with the h:g ratio ranging from 2 to 3, spinel oxides (for example, NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM''''O, where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof (for example, lithium titanate (Li4Ti5O 12 ) or lithium molybdate (Li2Mo4O 13 The compound may be selected from the following:

[0095] The negative electrode material may also optionally include conductive materials, binders, salts, inorganic particles, or combinations of two or more of these.

[0096] The present specification also relates to a battery or electrochemical accumulator comprising at least one of the electrochemical cells defined above. For example, the battery may be selected from lithium batteries, lithium ion batteries, sodium batteries, sodium ion batteries, potassium batteries, potassium ion batteries, magnesium batteries and magnesium ion batteries, preferably lithium batteries or lithium ion batteries.

[0097] The electrochemical cells and accumulators described herein are intended for use, for example, in nomadic devices such as mobile phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in renewable energy storage. EXAMPLES

[0098] The following examples are for illustrative purposes only and should not be construed as further limiting the scope of the invention as contemplated, which examples will be better understood with reference to the accompanying drawings.

[0099] Example 1 Preparation of the Composition

[0100] Compositions 1, 2 and 4 (comparative), as well as compositions 3 and 5-19, were prepared with the ingredients and proportions shown in Table 1, and the following abbreviations are used: - US'674: Hyperbranched polyethers (macromonomers) containing crosslinkable acrylate units in the terminal chains, as described in US Pat. No. 7,897,674. - PEGDA: Poly(ethylene glycol) diacrylate - PETA: Pentaerythritol tetraacrylate - TEGDVE: Tri(ethylene glycol) divinyl ether - EGDMA: Ethylene glycol dimethacrylate - DVB: Divinylbenzene (approximately 80% 1,4-divinylbenzene, 20% 1,2-divinylbenzene) - HNT: Natural aluminosilicate ceramic (Halloysite nanotubes) - LLZO: Lithium lanthanum zirconium oxide (Li7La3Zr2O 12 ) MT: 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, i.e.: [ka] - EDDET: 2,2'-(ethylenedioxy)diethanethiol - PTMP: pentaerythritol tetrakis(3-mercaptopropionate); and - TBT: 4,4'-thiobisbenzenethiol. [Table 1]

[0101] More specifically, compositions 1 to 19 in Table 1 are prepared according to the following procedure.

[0102] Composition 1: 1.4 g of US'674 and 0.7 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stirrer for 24 hours, no polymer is formed.

[0103] Composition 2: 1.4 g of US'674, 0.7 g of LiTFSI and 0.7 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stirrer for 24 hours, no polymer is formed.

[0104] Composition 3: 1.4 g of US'674, 0.7 g of HNT and 0.7 g of MT are mixed thoroughly in a flask under air at room temperature and the solution is stirred with a magnetic stirrer. After 3 hours, the solution becomes solid, indicating the formation of a polymer.

[0105] Composition 4: 1.4 g of US'674, 0.7 g of HNT and 0.7 g of LiTFSI are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stir bar for 24 hours, no polymer is formed.

[0106] Composition 5: 1.5 g of US'674, 0.36 g of HNT and 0.76 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stirrer. After 3 hours, the solution becomes solid, indicating the formation of a polymer.

[0107] Composition 6: 1.5 g of US'674, 0.76 g of HNT and 0.36 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stir bar. After 3 hours, the solution becomes solid, indicating the formation of a polymer.

[0108] Composition 7: 1.0 g of US'674, 1.0 g of HNT and 1.0 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stir bar. After 1 hour, the solution becomes solid, indicating the formation of a polymer.

[0109] Composition 8: 1.5 g of US'674, 0.19 g of HNT and 0.75 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stirrer. After 3 hours, the solution becomes solid, indicating the formation of a polymer.

[0110] Composition 9: 1.5 g of US'674, 0.75 g of HNT and 0.19 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stirrer. After 3 hours, the solution becomes solid, indicating the formation of a polymer.

[0111] Composition 10: 0.6 g of US'674, 1.2 g of HNT and 1.2 g of MT are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stirrer. After 30 minutes, the solution becomes solid, indicating the formation of a polymer.

[0112] Composition 11: 1.4 g PEGDA, 0.7 g HNT and 0.7 g MT are mixed thoroughly in a flask at room temperature under air and the solution is stirred using a magnetic stir bar. After 15 min, the solution becomes solid, indicating the formation of a polymer.

[0113] Composition 12: 1.4 g of PETA, 0.7 g of HNT and 0.7 g of MT are mixed thoroughly in a flask at room temperature under air and the solution is stirred using a magnetic stir bar. After 15 minutes, the solution becomes solid, indicating the formation of a polymer.

[0114] Composition 13: 1.4 g of TEGDVE, 0.7 g of HNT and 0.7 g of MT are mixed thoroughly in a flask under air at room temperature and the solution is stirred using a magnetic stir bar. After 15 minutes, the solution becomes solid, indicating the formation of a polymer.

[0115] Composition 14: 1.4 g of EGDMA, 0.7 g of HNT and 0.7 g of MT are mixed thoroughly in a flask at room temperature under air and the solution is stirred using a magnetic stir bar. After 15 minutes, the solution becomes solid, indicating the formation of a polymer.

[0116] Composition 15: 1.4 g of DVB, 0.7 g of HNT and 0.7 g of MT are mixed thoroughly in a flask at room temperature under air and the solution is stirred using a magnetic stir bar. After 48 hours, the solution becomes solid, indicating the formation of a polymer.

[0117] Composition 16: 1.4 g of US'674, 0.7 g of HNT and 0.7 g of EDDET are mixed thoroughly in a flask under air at room temperature and the solution is stirred with a magnetic stir bar. After 15 minutes, the solution becomes solid, indicating the formation of a polymer.

[0118] Composition 17: 1.4 g of US'674, 0.7 g of HNT and 0.7 g of PTMP are mixed thoroughly in a flask at room temperature under air, and the solution is stirred with a magnetic stir bar. After 15 minutes, the solution becomes solid, indicating the formation of a polymer.

[0119] Composition 18: 1.2 g of US'674 and 0.3 g of TBT are mixed thoroughly in a flask overnight at room temperature under air. When the solution is homogenous, 0.5 g of HNT is added with stirring. After 15 minutes, the solution becomes solid, indicating the formation of a polymer.

[0120] Composition 19: 1.4g of US'674 and 0.2g of TBT are mixed thoroughly in a flask overnight at room temperature under air. When the solution is homogeneous, 0.4g of LLZO is added with stirring. After 15 minutes, the solution becomes solid, indicating the formation of a polymer.

[0121] Example 2 Evaluation of composition properties

[0122] a) Interaction between LLZO and TBT

[0123] To investigate the polymerization mechanism, solid-state NMR analysis of TBT, LLZO and TBT / LLZO mixtures was carried out on a 500 MHz NMR spectrometer equipped with a 4 mm triple resonance probe up to 15 kHz using MAS (magic angle spinning). The TBT / LLZO mixture was prepared by grinding in a mortar. The results of LLZO and TBT / LLZO mixtures were analyzed. 6 Li NMR spectra and the TBT and TBT / LLZO mixtures 13 The C NMR spectrum is shown in Figure 1(a) and (b).

[0124] Figure 1(a) shows that the signal intensity of LLZO in the mixture is weaker than that of LLZO, suggesting that there is an interaction between LLZO and TBT that changes the chemical environment of Li ions in LLZO. Furthermore, Figure 1(b) shows that the peaks corresponding to the carbons next to the SH groups in the TBT / LLZO mixture are shifted, indicating that the -S - It is shown that an anion is formed.

[0125] Example 3 Preparation and properties of electrolyte films

[0126] a) Effect of cross-linking

[0127] i. Film preparation:

[0128] All manipulations are carried out in a glove box under argon (0.1 ppm H2O, 0.1 ppm O2). Two particle sizes (approximately 3 μm and less than 1 μm) of sulfide electrolyte (Li6PS5Cl) are mixed in a 90 / 10 weight ratio using a vortex.

[0129] The binder is formed by a 40 / 60 mixture by weight of (a) polymer US'674 with 0.5 wt % UV crosslinker, or (b) polymer US'674 containing 2 wt % TBT, or (c) polymer US'674 containing 4 wt % TBT, and an ionic plastic salt (1,1'-hexamethylenebis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide), dissolved in dichloromethane (DCM), respectively.

[0130] The weight ratio of sulfide to binder is 90 / 10. The amount of DCM is adjusted to make a good viscosity mixture. The resulting mixture is coated on a pre-degreased aluminum foil surface. After drying in a glove box, UV curing is carried out on the film surface containing a UV curing agent.

[0131] ii. Impedance measurements:

[0132] A 10 mm diameter disk of each film prepared in (i) was placed in a mold and compressed under a pressure of 2.8 T, then transferred to a closed conductivity cell under argon at a pressure of 5 MPa. The temperature was allowed to stabilize for approximately 1 hour. Two impedance measurements were recorded at each temperature from -10°C to 70°C, then cooled to 20°C for 15 minutes between each measurement. The results for electrolytes containing 0.5 wt% crosslinker UV (circles), 2 wt% TBT (triangles) and 4 wt% TBT (squares) are shown in Figure 2.

[0133] After in situ densification of sulfide ceramic films, creep of ionic plastic salt at 70°C (heating, lower curve) and lowering of temperature (upper curve), an improvement in the ionic conductivity of the films can be observed with the use of TBT and its increasing content. Indeed, crosslinking of the US'674 polymer as a monomer by UV crosslinking results in a polymer that is involved in ionic conductivity, but whose intrinsic ionic conductivity is lower than that of the sulfide ceramic particles. The addition of TBT, which bonds between the monomer chains of the US'674 polymer, gradually inhibits ionic conduction through the US'674 polymer. As a result, ionic conduction occurs only through the sulfide particles, explaining the improvement in impedance after creep of the ionic plastic salt in the case of ionic plastic salt, which allows a better distribution of the ionic plastic salt around the particles.

[0134] b) Effect of the presence of salt

[0135] i. Film preparation:

[0136] The films are prepared as in Example 3(a)(i), with the binder being a 40 / 60 by weight mixture of (a) polymer US'674 with 2 wt% TBT, or (b) polymer US'674 with 30:1 O:Li ratio and 2 wt% TBT in LiFSI, or (c) polymer US'674 with 20:1 O:Li ratio and 2 wt% TBT in LiFSI, dissolved in DCM, with an ionic plastic salt (1,1'-hexamethylenebis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide), respectively. The resulting mixture is coated onto a previously degreased aluminum surface.

[0137] ii. Impedance measurements:

[0138] After drying the films in the glove box, impedance measurements are performed as described above. The results are shown in Figure 3 for polymer US'674 with 2 wt% TBT (triangles), polymer US'674 with 30:1 O:Li ratio in LiFSI and 2 wt% TBT (stars), and polymer US'674 with 20:1 O:Li ratio in LiFSI and 2 wt% TBT (inverted triangles).

[0139] It can be observed that the ionic conductivity of the film decreases with the addition and increase of LiFSI salt. Normally, the addition of LiFSI salt increases the ionic conductivity of the US'674 polymer, as described in US Pat. No. 7,897,674. However, the opposite is observed here. This confirms that TBT can interfere with the ionic conductivity properties of the US'674 polymer as a monomer by interposing itself between the chains of the polymer. The reaction product of the US'674 polymer and TBT then acts as a support for the film and provides it with flexibility. In this way, the added LiFSI salt does not participate in the conductivity and therefore blocks this conduction as a dead material, since it does not react with the other components of the film.

[0140] Several modifications can be made to any of the above embodiments without departing from the intended scope of the invention. All references, patent or scientific literature referred to in this application are incorporated herein by reference in their entirety for all purposes.

Claims

1. A composition comprising a polymer and inorganic particles, wherein the polymer is a reaction product of at least one monomer comprising at least one polymerizable or crosslinkable functional group with an organic compound comprising one or more SH groups, preferably wherein the monomer is a compound of formula R 2 (X) m , where R 2 is an organic group, X is a polymerizable or crosslinkable group, and m represents the number of X groups linked to R 2 and is a number comprised within the range of 1 to 8, preferably 2 to 4, or wherein the monomer is a macromonomer comprising at least one crosslinkable segment comprising units of formula R 2 (X) m and optionally a non-crosslinkable polymer segment, and the polymer is preferably a polymer of random, block or alternating configuration.

2. A non-crosslinkable polymer segment is present and has formula I: 【Chemistry 23】 10. The composition of claim 1, [In the formula, R is a hydrogen atom, C １ ~C １０ Alkyl group or -(CH ２ -O-R ａ -R ｂ ) group, R ａ is (CH ２ -CH ２ -O) ｊ or (CH(CH ３ )-CH ２ -O) ｊ and R ｂ is a hydrogen atom or C １ ~C １０ is an alkyl group, i is an integer selected from the range of 2 to 200,000; j is an integer selected from the range of 0 to 100.

3. X is a polymerizable or crosslinkable group containing a double bond, preferably X is a group of formula -R 3 -C(R 4 )=CH 2 , R 3 is O, NH, OCH 2 , NHCH 2 , OC(O), NHC(O) or is absent forming a covalent bond between R 2 and C(R 4 ), R 4 is H, C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl, preferably H or C 1 -C 6 alkyl, preferably H or C 1 -C 3 alkyl, more preferably H or methyl, and polymer units derived from said monomers are of the formula: 【Chemistry 24】 wherein R 2 , R 3 , R 4 and m are as defined above; 【Chemistry 25】 represents a bond to a hydrogen atom, a bond to a sulfur atom from the organic compound, an end group, or another unit of the polymer when connected to C(R3R4) or CH2, and represents a macromonomer when adjacent to R2.

4. R ２ , or R ２ The macromonomer comprising linear or branched C ２～１２ 2. The composition of claim 1, wherein R 2 is selected from alkyl, alkylene oxide or poly(alkylene oxide), alkylene sulfide or poly(alkylene sulfide), siloxane or polysiloxane, and mono- or poly-aromatic group, or R 2 is selected from linear or branched C 2-12 alkyl, alkylene oxide or poly(alkylene oxide) and phenyl group.

5. 2. The composition of claim 1, wherein the monomer is selected from branched poly(ethylene glycol), poly(ethylene glycol) diacrylate, pentaerythritol tetraacrylate, triethylene glycol divinyl ether, ethylene glycol dimethacrylate, and divinylbenzene containing acrylate groups at the end of the main chain and / or side chains and / or on the chain.

6. The polymer units derived from the monomer have the formula: 【Chemistry 26】 The composition of claim 3, comprising at least one unit of [In the formula, R ４ and 【Chemistry 27】 is as defined in claim 3, and p is a number different from zero.

7. 7. The composition of any one of claims 1 to 6, wherein the monomer content in the composition ranges from about 1% to about 95% by weight, or from about 2% to about 90% by weight, or from about 3% to about 80% by weight, or from about 4% to about 50% by weight, or from about 10% to about 70% by weight, or from about 20% to about 65% by weight.

8. The organic compound is of formula R １ (SH) ｎ and R １ is an organic group linking the SH groups, and n is R １ represents the number of sulfur atoms linked to the compound of formula R １ (SH) ｎ Preferably, the polymer unit derived from the organic compound is a macromonomer comprising at least one segment comprising a unit of the formula: 【Chemistry 28】 wherein R 1 and n are as defined above; 【Chemistry 29】 when attached to a sulfur atom, represents a linkage to another polymer unit such as a unit derived from said monomer, and when adjacent to R 1 represents a macromonomer, preferably wherein the segment comprising R 1 or R 1 is selected from a linear or branched C 2-12 alkyl, a linear or branched C 2-12 alkyl polyol ether or ester, an alkylene oxide or poly(alkylene oxide), alkylene sulfide or poly(alkylene sulfide), optionally containing one or more sulfur atoms in the chain, a siloxane or polysiloxane, a heterocycle, a mono- or polycycloalkyl or heterocycloalkyl, a fused or unfused mono- or poly-cyclic aromatic or heteroaromatic ring, optionally containing a linking atom, or a combination thereof.

9. 9. The composition of claim 8, wherein the organic compound is selected from 1-(2-mercaptoethoxy-2-ethoxyethyl-2-thioethyl)-2-pyrrolidone, 2,2'-(ethylenedioxy)diethanethiol, pentaerythritol tetrakis(3-mercaptopropionate), and 4,4'-thiobisbenzenethiol.

10. The polymer units derived from the organic compound have the formula: 【Transformation 30】 The composition of claim 8, comprising at least one unit of [In the formula, 【Chemistry 31】 is as defined in claim 8].

11. 7. The composition according to claim 1, wherein the content of the organic compound in the composition is in the range of about 0.01% to about 60% by weight, or about 0.05% to about 50% by weight, or about 10% to about 30% by weight, or about 15% to about 40% by weight.

12. the inorganic particles comprise inorganic compounds of amorphous, ceramic or glass-ceramic type, for example oxide, sulfide or oxysulfide based, the inorganic compounds being natural or synthetic; The inorganic particles are preferably of the formula (e.g., M 7 La 3 Zr 2 O 12 , M (7-a) La 3 Zr 2 Al b O 12 , M (7-a) La 3 Zr 2 Ga b O 12 , M (7-a) La 3 Zr (2-b) Ta b O 12 and M (7-a) La 3 Zr (2-b) Nb b O 12 ); MLTaO (e.g., M 7 La 3 Ta 2 O 12 , M 5 La 3 Ta 2 O 12 and M 6 La 3 Ta 1.5 Y 0.5 O 12 ); MLSnO (e.g., M 7 La 3 Sn 2 O 12 ); MAGP (e.g., M 1+a Al a Ge 2-a (PO 4 ) 3 ); MATP (e.g., M 1+a Al a Ti 2-a (PO 4 ) 3 ); MLTiO (e.g., M 3a La (2 / 3-a) TiO 3 ); MZP (e.g., M a Zr b (PO 4 ) c ); MCZP (e.g., M a C a b Zr c (PO 4 ) d ); MGPS (e.g., M a Ge b P c S d such as M 10 GeP 2 S 12 ); MGPSO (e.g., M a Ge b P c S d O e ); MSiPS (e.g., M a Si b P c S d such as M 10 SiP 2 S 12 ); MSiPSO (e.g., M a Si b P c S d O e ); MSnPS (e.g., M a Sn b P c S d such as M 10 SnP 2 S 12 ); MSnPSO (e.g., M a Sn b P c S d O e ); MPS (e.g., M a P b Sc such as M 7 P 3 S 11 ); MPSO (e.g., M a P b Sc O d ); MZPS (e.g., M a Zn b P c S d ); MZPSO (e.g., M a Zn b P c S d O e ); 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 ; S-yM 2 O-zP 2 S 5 ;xM 2 S-yM 2 O-zP 2 S 5 -wMX;xM₂S - yM₂O - zP₂S₅ - wP₂O₅; xM₂S - yM₂O - zP₂S₅ - wP₂O₅ - vMX; xM₂S - ySiS₂; MPSX (such as MaPbScXd like M₇P₃S₁₁X, M₇P₂S₈X and M₆PS₅X); MPSOX (such as MaPbScOdXe); MGPSX (Ma GebPcSdXe); MGPSOX (Ma GebPcSdOeXf); MSiPSX (Ma SibPcSdXe); MSiPSOX (Ma SibPcSdOeXf); MSnPSX (Ma SnbPcSdXe); MSnPSOX (Ma SnbPcSdOeXf); MZPSX (Ma ZnbPcSdXe); MZPSOX (Ma ZnbPcSdOeXf); M₃OX; M₂HOX; M₃PO₄; M₃PS₄; and inorganic compounds of MaPObNc (a = 2b + 3c - 5); [In the formula, M is one of an alkali metal, an alkaline earth metal, or a combination thereof, and when M comprises an alkaline earth metal ion, the number of M is adjusted to achieve electroneutrality; X is selected from F, Cl, Br, I, or combinations thereof; a, b, c, d, e, and f are numbers different from zero and are independently selected in each formula to achieve electroneutrality; v, w, x, y, and z are numbers different from zero and are independently selected in each formula to provide a stable compound. wherein the ceramic MLZO is preferably of the formula Li 7-b La 3 Zr 2 M i b O 12 , where b is 0≦b≦1 and M i is Al, Ga, Ta, Fe or Nb or is absent, preferably b is 0 and M i is absent, or The inorganic particles are preferably selected from Al 2 O 3 , Mg 2 B 2 O 5 , Na 2 O·2B 2 O 3 , xMgO·yB 2 O 3 ·zH 2 O, TiO 2 , ZrO 2 , ZnO, Ti 2 O 3 , SiO 2 , Cr 2 O 3 , CeO 2 , B 2 O 3 , B 2 O, SrBi 4 Ti 4 O 15 , LLTO, LLZO, LAGP, LATP, Fe 2 O 3 , BaTiO 3 , γ-LiAlO 2 , molecular sieves and zeolites (e.g., aluminosilicates, mesoporous silica), sulfide ceramics (e.g., Li 6 PS 5 Cl, Li 7 P 3 S 11 ), glass-ceramics (such as LIPON) and other ceramics, and combinations thereof, and preferably the ceramic is an aluminosilicate compound; or the ceramic is preferably a sulfide or oxysulfide based ceramic, and / or The composition of any one of claims 1 to 6, wherein the inorganic particles are in the form of particles that are one of spheres, rods, needles, nanotubes, or combinations thereof.

13. 7. The composition of any one of claims 1 to 6, wherein the content of inorganic particles in the composition is in the range of about 5% to about 99% by weight, or about 5% to about 90% by weight, or about 10% to about 80% by weight, or about 15% to about 40% by weight.

14. The composition of any one of claims 1 to 6, wherein the composition is solid and / or the composition does not contain a polymerization initiator or a crosslinking agent.

15. 7. A method for preparing a composition as defined in any one of claims 1 to 6, comprising the step of mixing inorganic particles, at least one monomer comprising at least one polymerizable or crosslinkable functional group, and an organic compound comprising one or more SH groups.

16. 16. The method of claim 15, wherein the mixing step is carried out at a temperature in the range of 15°C to 50°C, or in the range of 20°C to 35°C, or in the range of 20°C to 30°C, and / or the mixing step is carried out in the presence of oxygen (e.g., in air) or under an inert atmosphere, and / or the method does not include the addition of a polymerization initiator or a crosslinking agent.

17. 16. The method of claim 15, further comprising the step of applying the resulting mixture to a surface of a support, preferably wherein the support is an inert film and the method optionally comprises the step of removing the film, alternatively wherein the support is an electrode film, alternatively wherein the support is a current collector or an electrolyte film.

18. An electrolyte comprising a composition as defined in any one of claims 1 to 6, preferably in the form of a solid electrolyte film.

19. 7. An electrode comprising a composition as defined in any one of claims 1 to 6 and an electrochemically active material, optionally a current collector, and optionally a conductive material, a binder, a salt or a combination of two or more thereof.

20. The electrochemically active material is LiM'PO ４ (M' is Fe, Ni, Mn, Co or a combination thereof), LiV ３ O ８ , V ２ O ５ F, LiV ２ O ５ , LiMn ２ O ４ , LiM''O ２ (M″ is Mn, Co, Ni or a combination thereof (NMC, LiMn ｓ Co ｔ Ni ｕ O ２ etc., where s+t+u=1), Li(NiM′″)O ２ 20. The electrode of claim 19, wherein M''' is an electrochemically active positive electrode material such as elemental sulfur, selenium or iodine, iron (III) fluoride, copper (II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material, or a combination of two or more of these materials, if compatible with each other.

21. 19. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the electrolyte is as defined in claim 18, and wherein the positive electrode comprises an electrochemically active positive electrode material, optionally on a current collector surface, the positive electrode material optionally further comprising a conductive material, a binder, a salt and / or inorganic particles.

22. The electrochemically active positive electrode material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides; or the electrochemically active positive electrode material is selected from LiM'PO4 (where M' is Fe, Ni, Mn, Co, or a combination thereof), LiV3O8, V2O5F, LiV2O5, LiMn2O4, LiM''O2 (where M'' is Mn, Co, Ni, or a combination thereof (such as NMC, LiMn5CotNiuO2, where s+t+u=1), Li(NiM''')O2 22. The electrochemical cell of claim 21 , wherein M′″ is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof, elemental sulfur, selenium, or iodine, iron (III) fluoride, copper (II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material, or a combination of two or more of these materials if compatible with each other.

23. 22. The electrochemical cell of claim 21, wherein the electrolyte is in direct contact with the positive electrode and / or the negative electrode, preferably with the positive electrode.

24. 20. An electrochemical cell comprising a negative electrode, a positive electrode and an electrolyte, wherein the positive electrode is as defined in claim 19.

25. 22. The electrochemical cell of claim 21 , wherein the negative electrode comprises an electrochemically active negative electrode material, optionally a current collector, and optionally a conductive material, a binder, a salt, inorganic particles, or a combination of two or more thereof.

26. The electrochemically active negative electrode material may comprise a metal film comprising an alkali metal or alkaline earth metal, or an alloy containing an alkali metal or alkaline earth metal, preferably the alkali metal being selected from lithium and sodium, or an alloy containing one of these; or the electrochemically active negative electrode material may comprise a metal film selected from an intermetallic compound (e.g., SnSb, TiSnSb, Cu 2 Sb, AlSb, FeSb 2 , FeSn 2 , and CoSn 2 ), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiTi 2 (PO 4 ) 3 ), a metal halide (e.g., a metal fluoride), a metal sulfide, a metal oxysulfide, carbon (e.g., graphite, graphene, reduced graphene oxide, hard carbon, soft carbon, exfoliated graphite, and amorphous carbon), silicon (Si), a silicon-carbon composite (Si—C), a silicon oxide (SiO x ), 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 thereof, where compatible, preferably the metal oxide is of the formula M''''gOh (M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof, and g and h are numbers with the h:g ratio in the range of 2 to 3) (e.g., MoO 3 , MoO 2 , MoS 2 , V 2 O 5 and TiNb 2 O 7 ), spinel oxides (e.g., NiCo 2 O 4 , ZnCo 2 O 4 , MnCo 2 O 4 , CuCo 2 O 7 ), 4 and CoFe2O4) and LiM'''''O (M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb or a combination thereof) (e.g., lithium titanate (such as Li4Ti5O12) or lithium molybdate (such as Li2Mo4O13)).

27. 22. A battery comprising at least one electrochemical cell as defined in claim 21, wherein said battery is preferably selected from lithium batteries, lithium ion batteries, sodium batteries, sodium ion batteries, potassium batteries, potassium ion batteries, magnesium batteries and magnesium ion batteries, more preferably a lithium battery or a lithium ion battery.

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