Electrolyte membrane for battery cycling lithium

Abstract

The invention discloses an electrolyte membrane for a lithium ion cycling battery and a manufacturing method thereof. An electrolyte membrane for a battery that circulates lithium ions includes a sulfide-based solid electrolyte, a polymer binder, an inorganic filler, an inorganic lithium salt, and an ionic liquid. The sulfide-based solid electrolyte contains lithium sulfide (Li2S) and at least one element selected from the group consisting of phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga), and aluminum (Al). The ionic liquid comprises substantially equimolar amounts of cations and anions. The cations include a complex of lithium (Li +) and ethylene glycol dimethyl ether, an imidazolium ion, a piperidinium ion, a pyrrolidinium ion, an ammonium ion, a phosphonium ion, or a combination thereof. The anions include arsenate ions, phosphate ions, sulfimide ions, borate ions, chlorate ions, or a combination thereof.

Description

Technical Field

[0001] The present disclosure relates to electrolytes for batteries that cycle lithium ions, and more particularly, to electrolyte membranes comprising a sulfide-based solid electrolyte and an ionic liquid. Background Art

[0002] The information provided in this section is for the purpose of generally presenting the background of the present disclosure. The work of the presently named inventors, to the extent described in this section and in all aspects of the description that might not otherwise constitute prior art at the time of filing, is neither expressly nor impliedly admitted as prior art to the present disclosure.

[0003] The present disclosure relates to electrolytes for batteries that cycle lithium ions, and more particularly, to electrolyte membranes comprising a sulfide-based solid electrolyte and an ionic liquid.

[0004] Batteries that cycle lithium ions typically include a negative electrode, a positive electrode, and an electrolyte that provides a medium for lithium ion conduction between the negative and positive electrodes. Sulfide-based solid electrolytes are promising candidates because they are able to establish intimate interfacial contact with electrode materials and they have excellent ionic conductivity at room temperature. Summary of the invention

[0005] The present invention discloses an electrolyte membrane for a battery for circulating lithium ions. The electrolyte membrane comprises a sulfide-based solid electrolyte, a polymer binder, an inorganic filler, an inorganic lithium salt and an ionic liquid. The sulfide-based solid electrolyte comprises lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga) and aluminum (Al). The ionic liquid comprises substantially equimolar amounts of cations and anions. The cations include lithium (Li + ) and ethylene glycol dimethyl ether, imidazolium ion, piperidinium ion, pyrrolidinium ion, ammonium ion, phosphonium ion or a combination thereof. The anion includes arsenate ion, phosphate ion, sulfonimide ion, borate ion, chlorate ion or a combination thereof.

[0006] The cations in the ionic liquid may include lithium (Li + ) and triethylene glycol dimethyl ether complex; lithium (Li +) and tetraethylene glycol dimethyl ether complex; 1-ethyl-3-methylimidazolium; 1-propyl-3-methylimidazolium; 1-butyl-3-methylimidazolium; 1,2-dimethyl-3-butylimidazolium; 1-alkyl-3-methylimidazolium, 1-allyl-3-methylimidazolium; 1,3-diallylimidazolium; 1-allyl-3-vinylimidazolium; 1-vinyl-3-ethylimidazolium; 1-cyanomethyl-3-methylimidazolium; 1,3-dicyanomethyl-imidazolium; 1-propyl-1-methylpiperidinium; 1-butyl-1-methylpiperidinium ; 1-methyl-1-ethylpyrrolidinium; 1-propyl-1-methylpyrrolidinium; 1-butyl-1-methylpyrrolidinium; methyl-methylcarboxymethyl-pyrrolidinium; tetramethylammonium; tetraethylammonium; tributylmethylammonium; diallyldimethylammonium; N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium; N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium; trimethylisobutylphosphonium; triisobutylmethylphosphonium; tributylmethylphosphonium; diethylmethylisobutylphosphonium; trihexyldecylphosphonium; trihexyltetradecylphosphonium; or a combination thereof.

[0007] The anions in the ionic liquid may include hexafluoroarsenate, hexafluorophosphate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, perchlorate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, bis(perfluoroethanesulfonyl)imide, bis(oxalato)borate, difluorooxalatoborate, bis(fluoromalonato)borate, or a combination thereof.

[0008] The ionic liquid may further include a diluent selected from the group consisting of dimethyl carbonate, ethylene carbonate, ethyl acetate, acetone, acetonitrile, toluene, propylene carbonate, diethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, and combinations thereof.

[0009] The sulfide-based solid electrolyte may include lithium sulfide (Li2S) and at least one additional inorganic compound selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), arsenic sulfide (As2S5) and manganese sulfide (MnS).

[0010] The sulfide-based solid electrolyte may comprise a binary sulfide comprising lithium sulfide (Li2S) and at least one additional sulfide selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3) and aluminum sulfide (Al2S3).

[0011] The sulfide-based solid electrolyte may include a ternary sulfide comprising lithium sulfide (Li2S) and at least two additional inorganic compounds selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI) and arsenic sulfide (As2S5).

[0012] The sulfide-based solid electrolyte may include a quaternary sulfide comprising lithium sulfide (Li2S) and at least three additional inorganic compounds selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium chloride (LiCl), lithium iodide (LiI) and manganese sulfide (MnS).

[0013] The polymer binder may include polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), styrene-butadiene rubber (SBR), polystyrene-block-poly(ethylene-random-butylene)-block-polystyrene (SEBS), or a combination thereof.

[0014] The inorganic filler may include alumina (Al2O3), silicon dioxide (SiO2), or a combination thereof.

[0015] The inorganic lithium salt may include lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2) (LiFSI), or a combination thereof.

[0016] In some aspects, the sulfide-based solid electrolyte may include lithium phosphorus sulfur chloride (Li6PS5Cl), the polymer binder may include polyethylene oxide, the inorganic filler may include alumina, the inorganic lithium salt may include lithium bis(fluorosulfonyl)imide, and the ionic liquid may include substantially equimolar amounts of (i) lithium (Li+ ) complex with tetraethylene glycol dimethyl ether and (ii) bis(trifluoromethanesulfonyl)imide.

[0017] The electrolyte membrane may have a thickness of greater than or equal to about 5 micrometers and less than or equal to about 500 micrometers.

[0018] The present invention discloses a battery for circulating lithium ions. The battery comprises a negative electrode comprising an electroactive negative electrode material, a positive electrode spaced apart from the negative electrode and comprising an electroactive positive electrode material, and an electrolyte membrane disposed between the negative electrode and the positive electrode, wherein the electrolyte membrane provides a medium for lithium ion conduction between the negative electrode and the positive electrode. The electrolyte membrane comprises a sulfide-based solid electrolyte, a polymer binder, an inorganic filler, an inorganic lithium salt, and an ionic liquid. The sulfide-based solid electrolyte comprises lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga), and aluminum (Al). The ionic liquid comprises cations and anions in substantially equimolar amounts. The cations comprise lithium (Li2S). + ) and ethylene glycol dimethyl ether, imidazolium ion, piperidinium ion, pyrrolidinium ion, ammonium ion, phosphonium ion or a combination thereof. The anion includes arsenate ion, phosphate ion, sulfonimide ion, borate ion, chlorate ion or a combination thereof.

[0019] The ionic liquid may contain lithium (Li + ) and triethylene glycol dimethyl ether complex; lithium (Li + ) and tetraethylene glycol dimethyl ether complex; 1-ethyl-3-methylimidazolium; 1-propyl-3-methylimidazolium; 1-butyl-3-methylimidazolium; 1,2-dimethyl-3-butylimidazolium; 1-alkyl-3-methylimidazolium, 1-allyl-3-methylimidazolium; 1,3-diallylimidazolium; 1-allyl-3-vinylimidazolium; 1-vinyl-3-ethylimidazolium; 1-cyanomethyl-3-methylimidazolium; 1,3-dicyanomethyl-imidazolium; 1-propyl-1-methylpiperidinium; 1-butyl-1-methylpiperidinium ; 1-methyl-1-ethylpyrrolidinium; 1-propyl-1-methylpyrrolidinium; 1-butyl-1-methylpyrrolidinium; methyl-methylcarboxymethyl-pyrrolidinium; tetramethylammonium; tetraethylammonium; tributylmethylammonium; diallyldimethylammonium; N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium; N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium; trimethylisobutylphosphonium; triisobutylmethylphosphonium; tributylmethylphosphonium; diethylmethylisobutylphosphonium; trihexyldecylphosphonium; trihexyltetradecylphosphonium; or a combination thereof.

[0020] The anions in the ionic liquid may include hexafluoroarsenate, hexafluorophosphate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, perchlorate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, bis(perfluoroethanesulfonyl)imide, bis(oxalato)borate, difluorooxalatoborate, bis(fluoromalonato)borate, or a combination thereof.

[0021] The sulfide-based solid electrolyte may include lithium sulfide (Li2S) and at least one additional inorganic compound selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), arsenic sulfide (As2S5) and manganese sulfide (MnS).

[0022] The polymer binder may include polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), styrene-butadiene rubber (SBR), polystyrene-block-poly(ethylene-random-butylene)-block-polystyrene (SEBS), or a combination thereof.

[0023] The inorganic filler may include alumina (Al2O3), silicon dioxide (SiO2), or a combination thereof.

[0024] The inorganic lithium salt may include lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2) (LiFSI), or a combination thereof.

[0025] The present invention discloses a method for manufacturing an electrolyte membrane for a battery for circulating lithium ions. In the method, a precursor mixture is prepared and deposited on a substrate to form a precursor layer. The precursor mixture comprises a sulfide-based solid electrolyte, a polymer binder, an inorganic filler, an inorganic lithium salt, an ionic liquid and a solvent. The sulfide-based solid electrolyte comprises lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga) and aluminum (Al). The ionic liquid comprises substantially equimolar amounts of cations and anions. The cations include lithium (Li +) and ethylene glycol dimethyl ether, imidazolium ion, piperidinium ion, pyrrolidinium ion, ammonium ion, phosphonium ion or a combination thereof. The anion includes arsenate ion, phosphate ion, sulfonimide ion, borate ion, chlorate ion or a combination thereof. After the precursor mixture is deposited on a substrate to form a precursor layer, the solvent is removed from the precursor layer to form an electrolyte membrane.

[0026] The present invention discloses the following embodiments:

[0027] 1. An electrolyte membrane for a battery for circulating lithium ions, the electrolyte membrane comprising:

[0028] A sulfide-based solid electrolyte comprising lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga) and aluminum (Al);

[0029] polymer binders;

[0030] Inorganic fillers;

[0031] Inorganic lithium salts; and

[0032] An ionic liquid comprising substantially equimolar amounts of cations and anions, the cations comprising lithium (Li + ) and ethylene glycol dimethyl ether, an imidazolium ion, a piperidinium ion, a pyrrolidinium ion, an ammonium ion, a phosphonium ion or a combination thereof, and the anion includes an arsenate ion, a phosphate ion, a sulfonimide ion, a borate ion, a chlorate ion or a combination thereof.

[0033] 2. The electrolyte membrane according to claim 1, wherein the cations in the ionic liquid include lithium (Li + ) and triethylene glycol dimethyl ether complex; lithium (Li +) and tetraethylene glycol dimethyl ether complex; 1-ethyl-3-methylimidazolium; 1-propyl-3-methylimidazolium; 1-butyl-3-methylimidazolium; 1,2-dimethyl-3-butylimidazolium; 1-alkyl-3-methylimidazolium, 1-allyl-3-methylimidazolium; 1,3-diallylimidazolium; 1-allyl-3-vinylimidazolium; 1-vinyl-3-ethylimidazolium; 1-cyanomethyl-3-methylimidazolium; 1,3-dicyanomethyl-imidazolium; 1-propyl-1-methylpiperidinium; 1-butyl-1-methylpiperidinium ; 1-methyl-1-ethylpyrrolidinium; 1-propyl-1-methylpyrrolidinium; 1-butyl-1-methylpyrrolidinium; methyl-methylcarboxymethyl-pyrrolidinium; tetramethylammonium; tetraethylammonium; tributylmethylammonium; diallyldimethylammonium; N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium; N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium; trimethylisobutylphosphonium; triisobutylmethylphosphonium; tributylmethylphosphonium; diethylmethylisobutylphosphonium; trihexyldecylphosphonium; trihexyltetradecylphosphonium; or a combination thereof.

[0034] 3. An electrolyte membrane according to Scheme 1, wherein the anions in the ionic liquid include hexafluoroarsenate, hexafluorophosphate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, perchlorate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, bis(perfluoroethanesulfonyl)imide, bis(oxalato)borate, difluorooxalatoborate, bis(fluoromalonate)borate or a combination thereof.

[0035] 4. The electrolyte membrane according to scheme 1, wherein the ionic liquid further comprises a diluent, and the diluent is selected from dimethyl carbonate, ethylene carbonate, ethyl acetate, acetone, acetonitrile, toluene, propylene carbonate, diethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether and combinations thereof.

[0036] 5. An electrolyte membrane according to Option 1, wherein the sulfide-based solid electrolyte comprises lithium sulfide (Li2S) and at least one additional inorganic compound, the additional inorganic compound being selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), arsenic sulfide (As2S5) and manganese sulfide (MnS).

[0037] 6. An electrolyte membrane according to Option 1, wherein the sulfide-based solid electrolyte comprises a binary sulfide, the binary sulfide comprising lithium sulfide (Li2S) and at least one additional sulfide, the additional sulfide being selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3) and aluminum sulfide (Al2S3).

[0038] 7. An electrolyte membrane according to Option 1, wherein the sulfide-based solid electrolyte comprises a ternary sulfide, the ternary sulfide comprising lithium sulfide (Li2S) and at least two additional inorganic compounds, the additional inorganic compounds being selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI) and arsenic sulfide (As2S5).

[0039] 8. An electrolyte membrane according to Scheme 1, wherein the sulfide-based solid electrolyte comprises a quaternary sulfide, the quaternary sulfide comprising lithium sulfide (Li2S) and at least three additional inorganic compounds, the additional inorganic compounds being selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium chloride (LiCl), lithium iodide (LiI) and manganese sulfide (MnS).

[0040] 9. An electrolyte membrane according to Scheme 1, wherein the polymer binder comprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), styrene-butadiene rubber (SBR), polystyrene-block-poly(ethylene-random-butylene)-block-polystyrene (SEBS) or a combination thereof.

[0041] 10. The electrolyte membrane according to claim 1, wherein the inorganic filler comprises aluminum oxide (Al2O3), silicon dioxide (SiO2), or a combination thereof.

[0042] 11. An electrolyte membrane according to Scheme 1, wherein the inorganic lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2) (LiFSI) or a combination thereof.

[0043] 12. An electrolyte membrane according to claim 1, wherein the sulfide-based solid electrolyte comprises lithium phosphorus sulfur chloride (Li6PS5Cl), the polymer binder comprises polyethylene oxide, the inorganic filler comprises aluminum oxide, the inorganic lithium salt comprises lithium bis(fluorosulfonyl)imide, and the ionic liquid comprises substantially equimolar amounts of (i) lithium (Li + ) complex with tetraethylene glycol dimethyl ether and (ii) bis(trifluoromethanesulfonyl)imide.

[0044] 13. The electrolyte membrane according to claim 1, wherein the electrolyte membrane has a thickness of greater than or equal to about 5 micrometers and less than or equal to about 500 micrometers.

[0045] 14. A battery for circulating lithium ions, the battery comprising:

[0046] a negative electrode comprising an electroactive negative electrode material;

[0047] a positive electrode spaced apart from the negative electrode and comprising an electroactive positive electrode material; and

[0048] An electrolyte membrane disposed between the negative electrode and the positive electrode, which provides a medium for lithium ion conduction between the negative electrode and the positive electrode, the electrolyte membrane comprising:

[0049] A sulfide-based solid electrolyte comprising lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga) and aluminum (Al);

[0050] polymer binders;

[0051] Inorganic fillers;

[0052] Inorganic lithium salts; and

[0053] An ionic liquid comprising substantially equimolar amounts of cations and anions, the cations comprising lithium (Li + ) and ethylene glycol dimethyl ether, an imidazolium ion, a piperidinium ion, a pyrrolidinium ion, an ammonium ion, a phosphonium ion or a combination thereof, and the anion includes an arsenate ion, a phosphate ion, a sulfonimide ion, a borate ion, a chlorate ion or a combination thereof.

[0054] 15. A battery according to claim 14, wherein the cations in the ionic liquid include lithium (Li + ) and triethylene glycol dimethyl ether complex; lithium (Li +) and tetraethylene glycol dimethyl ether; 1-ethyl-3-methylimidazolium; 1-propyl-3-methylimidazolium; 1-butyl-3-methylimidazolium; 1,2-dimethyl-3-butylimidazolium; 1-alkyl-3-methylimidazolium, 1-allyl-3-methylimidazolium; 1,3-diallylimidazolium; 1-allyl-3-vinylimidazolium; 1-vinyl -3-ethylimidazolium; 1-cyanomethyl-3-methylimidazolium; 1,3-dicyanomethyl-imidazolium; 1-propyl-1-methylpiperidinium; 1-butyl-1-methylpiperidinium; 1-methyl-1-ethylpyrrolidinium; 1-propyl-1-methylpyrrolidinium; 1-butyl-1-methylpyrrolidinium; methyl-methylcarboxymethyl-pyrrolidinium; tetramethylammonium; tetraethylammonium ; tributylmethylammonium; diallyldimethylammonium; N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium; N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium; trimethylisobutylphosphonium; triisobutylmethylphosphonium; tributylmethylphosphonium; diethylmethylisobutylphosphonium; trihexyldecylphosphonium; trihexyltetradecylphosphonium; or a combination thereof, and wherein the anion in the ionic liquid comprises hexafluoroarsenate, hexafluorophosphate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, perchlorate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, bis(perfluoroethanesulfonyl)imide, bis(oxalato)borate, difluorooxalatoborate, bis(fluoromalonato)borate, or a combination thereof.

[0055] 16. A battery according to embodiment 14, wherein the sulfide-based solid electrolyte comprises lithium sulfide (Li2S) and at least one additional inorganic compound, wherein the additional inorganic compound is selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), arsenic sulfide (As2S5) and manganese sulfide (MnS).

[0056] 17. A battery according to embodiment 14, wherein the polymer binder comprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), styrene-butadiene rubber (SBR), polystyrene-block-poly(ethylene-random-butylene)-block-polystyrene (SEBS) or a combination thereof.

[0057] 18. A battery according to Option 14, wherein the inorganic filler comprises aluminum oxide (Al2O3), silicon dioxide (SiO2) or a combination thereof.

[0058] 19. A battery according to Option 14, wherein the inorganic lithium salt includes lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2) (LiFSI) or a combination thereof.

[0059] 20. A method of manufacturing an electrolyte membrane for a battery for cycling lithium ions, the method comprising:

[0060] (a) preparing a precursor mixture comprising:

[0061] A sulfide-based solid electrolyte comprising lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga) and aluminum (Al);

[0062] polymer binders;

[0063] Inorganic fillers;

[0064] Inorganic lithium salts;

[0065] An ionic liquid comprising substantially equimolar amounts of cations and anions, the cations comprising lithium (Li + ) and ethylene glycol dimethyl ether, an imidazolium ion, a piperidinium ion, a pyrrolidinium ion, an ammonium ion, a phosphonium ion or a combination thereof, and the anion comprises an arsenate ion, a phosphate ion, a sulfonimide ion, a borate ion, a chlorate ion or a combination thereof; and

[0066] Solvents;

[0067] (b) depositing the precursor mixture on a substrate to form a precursor layer;

[0068] (c) removing the solvent from the precursor layer to form the electrolyte membrane.

[0069] Further areas of applicability of the present disclosure will become apparent from the detailed description, claims and drawings.The detailed description and specific examples are intended for illustrative purposes only and are not intended to limit the scope of the present disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] The present disclosure will be more fully understood from the detailed description and accompanying drawings, in which:

[0071] Figure 1 is a schematic perspective view of a motor vehicle powered by a battery pack including a plurality of battery modules.

[0072] Figure 2 yes Figure 1Schematic cross-sectional view of a portion of one of the battery modules of FIG. 1 , the battery module comprising a plurality of cycling lithium-ion electrochemical cells or batteries.

[0073] Figure 3 is a schematic cross-sectional view of a battery that circulates lithium ions, the battery including a positive electrode, a negative electrode, and an electrolyte membrane disposed between the positive electrode and the negative electrode.

[0074] Figure 4 yes Figure 3 Detailed view of the electrolyte membrane.

[0075] Among the drawings, reference numerals may be repeated to identify similar and / or identical elements. DETAILED DESCRIPTION

[0076] The electrolyte membrane of the present disclosure is formulated for use in batteries that cycle lithium ions and comprises a sulfide-based solid electrolyte, a polymer binder, an inorganic filler, an inorganic lithium salt, and an ionic liquid. The inclusion of an ionic liquid in the electrolyte membrane increases the ionic conductivity of the electrolyte membrane without changing the chemical composition or crystal structure of the sulfide-based solid electrolyte.

[0077] Figure 1 A motor vehicle 2 is depicted that is powered by an electric motor 4 that draws power from a battery pack 6 that includes one or more battery modules 8. The battery modules 8 may be electrically connected together in a series and / or parallel arrangement to meet the desired capacity and power requirements of the electric motor 4. The vehicle 2 may be a pure electric vehicle and may be powered solely by the electric motor 4, or the vehicle 2 may be a hybrid electric vehicle and may be powered by both the electric motor 4 and an internal combustion engine (not shown).

[0078] like Figure 2 As shown, each battery module 8 includes one or more electrochemical cells or batteries 10 that circulate lithium ions. In practice, the batteries 10 in the battery module 8 are often assembled as a stack of layers, including a negative electrode layer 12, a negative electrode current collector 13, a positive electrode layer 14, a positive electrode current collector 15, and a separator layer 16. Each battery 10 is defined by a negative electrode layer 12 and a positive electrode layer 14, which are separated from each other by a separator layer 16. In practice, the separator layer 16 can be impregnated with an electrolyte that provides a medium for lithium ion conduction between the negative electrode layer 12 and the positive electrode layer 14, or the separator layer 16 itself can act as an electrolyte. The negative electrode layer 12 is disposed on and electrically connected to the negative electrode current collector 13, and the positive electrode layer 14 is disposed on and electrically connected to the positive electrode current collector 15. As shown in FIG. Figure 2As shown, for efficiency, these layers can be stacked so that some of the negative electrode collectors 13 and the positive electrode collectors 15 are double-sided and include negative electrode layers 12 or positive electrode layers 14 on both sides thereof. In this arrangement, adjacent negative electrode layers 12 and positive electrode layers 14 share a single negative electrode collector 13 or positive electrode collector 15.

[0079] Figure 3 An electrochemical cell or battery 20 of circulating lithium ions is depicted. The battery 20 can generate an electric current during discharge, which can be used to power a load device (e.g., the motor 4), and the battery 20 can be recharged by connecting to a power source. Figure 1 and 2 Similar to the battery 10 depicted in FIG, the battery 20 may be used to power the electric motor 4 of the motor vehicle 2. Additionally or alternatively, the battery 20 may be used in other transportation applications (e.g., motorcycles, boats, tractors, buses, motorbikes, mobile homes, campers, tanks, and aircraft), and may be used to power fixed and / or portable electronic devices, components, and devices used in a variety of other industries and applications, including, by way of non-limiting example, industrial, residential, and commercial buildings, consumer products, industrial equipment and machinery, agricultural or farm equipment, and heavy machinery.

[0080] The battery 20 includes a negative electrode 22, a positive electrode 24, and an electrolyte membrane 26 sandwiched between the negative electrode 22 and the positive electrode 24 and having a first side 38 and an opposing second side 40. The negative electrode 22 and the positive electrode 24 have opposing facing surfaces 42, 44, the facing surface 42 of the negative electrode 22 is in physical contact with the first side 38 of the electrolyte membrane 26, and the facing surface 44 of the positive electrode 24 is in physical contact with the second side 40 of the electrolyte membrane 26. The negative electrode 22 is disposed on a negative electrode current collector 30, and the positive electrode 24 is disposed on a positive electrode current collector 32.

[0081] In practice, the negative electrode current collector 30 and the positive electrode current collector 32 are electrically connected to a power source or load 34 (e.g., a motor 4) through an external circuit 36. The negative electrode 22 and the positive electrode 24 are configured to establish an electrochemical potential difference between the negative electrode 22 and the positive electrode 24 when the battery 20 is at least partially charged. During the discharge of the battery 20, the electrochemical potential established between the negative electrode 22 and the positive electrode 24 drives the spontaneous reduction and oxidation (redox) reactions within the battery 20 and the release of lithium ions and electrons at the negative electrode 22. The released lithium ions move from the negative electrode 22 to the positive electrode 24 through the separator 26 and the electrolyte membrane 26, while the electrons move from the negative electrode 22 to the positive electrode 24 through the external circuit 36, which generates an electric current. After the negative electrode 22 has been partially or completely depleted of lithium, the battery 20 can be charged by connecting the negative electrode 22 and the positive electrode 24 to the power source 34, which drives the non-spontaneous redox reactions within the battery 20 and the release of lithium ions and electrons from the positive electrode 24. The repeated discharge and charge of battery 20 may be referred to herein as a "cycle," where a full charge event followed by a full discharge event is considered a full cycle.

[0082] The electrolyte membrane 26 extends from the facing surface 42 of the negative electrode 22 to the facing surface 44 of the positive electrode 24 between the negative electrode 22 and the positive electrode 24. The electrolyte membrane 26 may have a thickness of greater than or equal to about 5 microns (μm), or optionally greater than or equal to about 20 μm, and less than or equal to about 500 μm, or optionally less than or equal to about 200 μm. The electrolyte membrane 26 is ion conductive and provides a medium for conducting lithium ions through the battery 20 between the negative electrode 22 and the positive electrode 24. In an embodiment, the electrolyte membrane 26 may act as a separator and may physically separate and electrically isolate the negative electrode 22 and the positive electrode 24 from each other while allowing lithium ions to pass through. The electrolyte membrane 26 may have an ionic conductivity greater than or equal to about 0.1 millisiemens / cm (mS / cm), optionally greater than or equal to about 0.2 mS / cm, or optionally greater than or equal to about 0.5 mS / cm, and less than or equal to about 20 mS / cm at room temperature (e.g., about 25°C). For example, in some aspects, the electrolyte membrane 26 can have an ionic conductivity greater than or equal to about 0.51 mS / cm at room temperature. Figure 4 As best shown in FIG. 2 , the electrolyte membrane 26 includes a sulfide-based solid electrolyte 46 , a polymer binder 48 , an inorganic filler 50 , an inorganic lithium salt 52 , and an ionic liquid 54 .

[0083] The sulfide-based solid electrolyte 46 is formulated to provide an electrolyte membrane 26 having high ionic conductivity and good interfacial contact with the facing surfaces 42, 44 of the negative electrode 22 and the positive electrode 24. The sulfide-based solid electrolyte 46 is at least partially crystalline and comprises lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga), and aluminum (Al). In some aspects, the sulfide-based solid electrolyte 46 can include Li2S and at least one additional inorganic compound selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), arsenic sulfide (As2S5), and manganese sulfide (MnS).

[0084] The sulfide-based solid electrolyte 46 may include a binary sulfide, a ternary sulfide, a quaternary sulfide, or a combination thereof. In aspects where the sulfide-based solid electrolyte 46 includes a binary sulfide, the sulfide-based solid electrolyte 46 may include lithium sulfide (Li2S) and at least one additional sulfide selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3), and aluminum sulfide (Al2S3). For example, the sulfide-based solid electrolyte 46 may include the following binary sulfides: Li2S-P2S5 (e.g., Li3PS4, Li7P3S 11 and Li 9.6 P3S 12), Li2S-SnS2 (e.g., Li4SnS4), Li2S-SiS2, Li2S-GeS2, Li2S-B2S3, Li2S-Ga2S3, Li2S-P2S3, Li2S-Al2S3, or a combination thereof. In aspects where the sulfide-based solid electrolyte 46 comprises a ternary sulfide, the sulfide-based solid electrolyte 46 may comprise lithium sulfide (Li2S) and at least two additional inorganic compounds selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), and arsenic sulfide (As2S5). For example, the sulfide-based solid electrolyte 46 may include the following ternary sulfides: Li2O-Li2S-P2S5, Li2S-P2S5-P2O5, Li2S-P2S5-GeS2 (e.g., Li 3.25 Ge 0.25 P 0.75 S4 and / or Li 10 GeP2S 12 ), Li2S-P2S5-LiX (wherein X is at least one of F, Cl, Br and I) (e.g., Li6PS5Br, Li6PS5Cl, L7P2S8I and / or Li4PS4I), Li2S-As2S5-SnS2 (e.g., Li 3.833 Sn 0.833 As 0.166 S4), Li2S-P2S5-Al2S3, Li2S-LiX-SiS2 (wherein X is at least one of F, Cl, Br and I), 0.4LiI·0.6Li4SnS4, Li 11 Si2PS 12 or a combination thereof. In aspects where the sulfide-based solid electrolyte 46 comprises a quaternary sulfide, the sulfide-based solid electrolyte 46 may comprise lithium sulfide (Li2S) and at least three additional inorganic compounds selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium chloride (LiCl), lithium iodide (LiI), and manganese sulfide (MnS). For example, the sulfide-based solid electrolyte may comprise the following quaternary sulfides: Li2O-Li2S-P2S5-P2O5, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 、Li7P 2.9 Mn0.1 S 10.7 I 0.3 , Li 10.35 [Sn 0.27 Si 1.08 ]P 1.65 S 12 In some aspects, the sulfide-based solid electrolyte 46 can include lithium phosphorus sulfur chloride Li6PS5Cl (LPSCl).

[0085] The sulfide-based solid electrolyte 46 may be a particulate material and may include particles having an average particle size of about 1 μm or more and about 20 μm or less. The sulfide-based solid electrolyte 46 may constitute about 70% or more, or optionally about 90% or more, and about 99% or less, or optionally about 95% or less by weight of the electrolyte membrane 26.

[0086] The polymer binder 48 is formulated to adhere the components of the electrolyte membrane 26 together and provide the electrolyte membrane 26 with robust mechanical properties and the ability to exist as a self-supporting membrane. The polymer binder 48 may include polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), styrene-butadiene rubber (SBR), polystyrene-block-poly (ethylene-random-butylene)-block-polystyrene (SEBS) or a combination thereof. In some aspects, the polymer binder 48 includes polyethylene oxide. The polymer binder 48 may constitute greater than or equal to about 3%, or optionally greater than or equal to about 4%, and less than or equal to about 20%, or optionally less than or equal to about 9% by weight of the electrolyte membrane 26.

[0087] The inorganic filler 50 is formulated to reduce the crystallinity of the polymer binder 48 and increase the ionic conductivity and the rate at which lithium ions are transported through the electrolyte membrane 26. The inorganic filler 50 may include aluminum oxide (Al2O3), silicon dioxide (SiO2), or a combination thereof. In some aspects, the inorganic filler 50 comprises aluminum oxide. The inorganic filler 50 may be a particulate material and may include particles having an average particle size greater than or equal to about 100 nanometers (nm) and less than or equal to about 10 μm. The inorganic filler 50 may constitute greater than or equal to 0%, or optionally greater than or equal to about 0.5%, and less than or equal to about 4%, or optionally less than or equal to about 1%, by weight of the electrolyte membrane 26.

[0088] The inorganic lithium salt 52 is formulated to increase the ionic conductivity of the electrolyte membrane 26 , for example, by creating lithium ion transport pathways through the polymer binder 48 . The inorganic lithium salt 52 may include lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalato)borate (LiB(C2O4)2) (LiBOB), lithium difluorooxalatoborate (LiBF2(C2O4)), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2) (LiFSI), lithium bis(trifluoromethanesulfonyl)amide (lithium bis(trifluoromethanesulfonyl)azanide, LiTFSA), or a combination thereof. In some aspects, the inorganic lithium salt 52 may include lithium bis(fluorosulfonyl)imide. The inorganic lithium salt 52 may constitute greater than or equal to 0%, or optionally greater than or equal to about 1%, and less than or equal to about 3%, or optionally less than or equal to about 2% by weight of the electrolyte membrane 26.

[0089] The ionic liquid 54 penetrates into the pores defined by and between the solid components of the electrolyte membrane 26, namely, the sulfide-based solid electrolyte 46, the polymer binder 48, the inorganic filler 50, and the inorganic lithium salt 52. Figure 4 As shown, the ionic liquid 54 can be disposed on the surface of the particles of the sulfide-based solid electrolyte 46, and can completely encapsulate the individual particles of the sulfide-based solid electrolyte 46. The ionic liquid 54 is formulated to have excellent chemical compatibility with the sulfide-based solid electrolyte 46, and improves the ionic conductivity of the electrolyte membrane 26, for example, by creating a lithium ion transfer path or "bridge" between the particles of the sulfide-based solid electrolyte 46. The ionic liquid 54 contains cations, anions, and an optional diluent. The cations and anions are present in the ionic liquid 54 in substantially equimolar amounts. The ionic liquid 54 can constitute greater than or equal to about 1%, or optionally greater than or equal to about 3%, and less than or equal to about 20%, or optionally less than or equal to about 7% by weight of the electrolyte membrane 26.

[0090] The cation of the ionic liquid 54 may include lithium (Li +) and ethylene glycol dimethyl ether (glyme), imidazolium ion, piperidinium ion, pyrrolidinium ion, ammonium ion, phosphonium ion or a combination thereof. Examples of glycol dimethyl ether include triethylene glycol dimethyl ether (triglyme) and tetraethylene glycol dimethyl ether (tetraglyme). In some aspects, the cation of the ionic liquid 54 may include lithium (Li + ) and triethylene glycol dimethyl ether complex, lithium (Li + ) and tetraethylene glycol dimethyl ether or a combination thereof. Examples of imidazolium ions include 1-ethyl-3-methylimidazolium ([Emim] + ); 1-propyl-3-methylimidazolium ([Pmim] + ); 1-butyl-3-methylimidazolium ([Bmim] + ); 1,2-dimethyl-3-butylimidazolium ([DMBim]); 1-alkyl-3-methylimidazolium ([Cnmim] + ), 1-allyl-3-methylimidazolium ([Amim] + ); 1,3-diallylimidazolium ([Daim] + ); 1-allyl-3-vinylimidazolium ([Avim] + ); 1-vinyl-3-ethylimidazolium ([Veim] + ); 1-cyanomethyl-3-methylimidazolium ([MCNim] + ); and 1,3-dicyanomethyl-imidazolium ([BCNim] + Examples of the piperidinium ion include 1-propyl-1-methylpiperidinium ([PP 13 ] + ) and 1-butyl-1-methylpiperidinium ([PP 14 ] + Examples of the pyrrolidinium ion include 1-methyl-1-ethylpyrrolidinium ([Pyr 12 ] + ); 1-propyl-1-methylpyrrolidinium ([Pyr 13 ] + ); 1-butyl-1-methylpyrrolidinium ([Pyr 14 ] + ); and methyl-methylcarboxymethyl-pyrrolidinium ([MMMPyr] + Examples of ammonium ions include tetramethylammonium ([N 1111 ] + ); tetraethylammonium ([N 2222 ] + ); tributylmethylammonium ([N 4441 ] + ); diallyldimethylammonium ([DADMA] +); N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium ([DEME] + ); and N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium ([DEMM] + Examples of phosphonium ions include trimethylisobutylphosphonium ([P 111i4 ] + ); triisobutylmethylphosphonium ([P 1i444 ] + ); tributylmethylphosphonium ([P 1444 ] + ); diethylmethylisobutylphosphonium ([P 1224 ] + ); and trihexyldecylphosphonium ([P 66610 ] + ); trihexyltetradecylphosphonium ([P 66614 ] + In some aspects, the cations in the ionic liquid 54 include lithium (Li + ) and tetraethylene glycol dimethyl ether complex.

[0091] The anions of the ionic liquid 54 may include arsenate ions, phosphate ions, sulfonimide ions, borate ions, chlorate ions, or combinations thereof. An example of an arsenate ion is hexafluoroarsenate (AsF6 - An example of a phosphate ion is hexafluorophosphate (PF6 - Examples of sulfonyl imide ions include bis(fluorosulfonyl)imide (N(FSO2)2 - )(FSI), bis(trifluoromethanesulfonyl)imide(N(CF3SO2)2 - )(TFSI), bis(perfluoroethanesulfonyl)imide (BETI - ), cyclo-difluoromethane-1,1-bis(sulfonyl)imide (DMSI - ) and combinations thereof. An example of a chlorate ion is perchlorate (ClO4 - Examples of borate ions include tetrafluoroborate (BF4 - ), bis(oxalato)borate (B(C2O4)2 - )(BOB), difluorooxalato borate (BF2(C2O4) - )(DFOB), bis(fluoromalonate)borate (BFMB - ) and combinations thereof. In some aspects, the anion of the ionic liquid 54 comprises bis(trifluoromethanesulfonyl)imide.

[0092] An optional diluent may be included in the ionic liquid 54 to reduce viscosity and improve lithium ion conductivity of the electrolyte membrane 26. The optional diluent may include a non-aqueous aprotic organic solvent. Non-limiting examples of non-aqueous aprotic organic solvents include cyclic carbonates (e.g., ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and / or fluoroethylene carbonate (FEC)), linear carbonates (e.g., dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC)), aliphatic carboxylates (e.g., methyl formate, ethyl acetate, methyl acetate, methyl propionate), γ-lactones (e.g., γ-butyrolactone, γ-valerolactone), chain structure ethers (e.g., 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane and / or 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether), cyclic ethers (e.g., tetrahydrofuran, 2-methyltetrahydrofuran), 1,3-dioxolane), acetone, acetonitrile and toluene.

[0093] In some aspects, the electrolyte membrane 26 may optionally include a halide-based solid electrolyte (not shown), a hydride-based solid electrolyte (not shown), or a combination thereof. Examples of halide-based solid electrolytes include Li3YCl6, Li3InCl6, Li3YBr6, LiI, Li2CdCl4, Li2MgCl4, Li2CdI4, Li2ZnI4, and / or Li3OCl. Examples of hydride-based solid electrolytes include LiBH4, LiBH4-LiX (X = Cl, Br or I), LiNH2, Li2NH, LiBH4-LiNH2, and / or Li3AlH6.

[0094] The positive electrode 24 is configured to reversibly store and release lithium ions during the discharge and charge process of the battery 20, and can be in the form of a continuous porous layer disposed on the major surface of the positive electrode current collector 32. The positive electrode 24 includes an electrochemically active (electroactive) material (electroactive positive electrode material), a polymer binder, and an optional conductive material. In some aspects, the electroactive material of the positive electrode 24 can be a particulate material, and the particles of the electroactive material of the positive electrode 24 can be intermixed with the polymer binder and the optional conductive material.

[0095] The electroactive material of the positive electrode 24 can store and release lithium ions by undergoing a reversible redox reaction with lithium at a higher electrochemical potential than the electrochemically active material of the negative electrode 22, so that there is an electrochemical potential difference between the negative electrode 22 and the positive electrode 24. The electroactive material of the positive electrode 24 may include a material capable of lithium intercalation and deintercalation or a material capable of undergoing a conversion reaction with lithium. In aspects where the electroactive material of the positive electrode 24 includes an intercalation host material capable of reversible insertion or embedding of lithium ions, the electroactive material of the positive electrode 24 may include a layered lithium transition metal oxide represented by the formula LiMeO2, an olivine-type lithium transition metal oxide represented by the formula LiMePO4, a monoclinic lithium transition metal oxide represented by the formula Li3Me2(PO4)3, a spinel-type lithium transition metal oxide represented by the formula LiMe2O4, tavorite represented by one or both of the following formulas LiMeSO4F or LiMePO4F, or a combination thereof, wherein Me is a transition metal (e.g., Co, Ni, Mn, Fe, Al, V, or a combination thereof). In aspects where the electroactive material of positive electrode 24 includes a conversion material, the electroactive material of positive electrode 24 may include sulfur, selenium, tellurium, iodine, halides (e.g., fluorides or chlorides), sulfides, selenides, tellurides, iodides, phosphides, nitrides, oxides, oxysulfides, oxyfluorides, sulfur-fluorides, sulfur-oxyfluorides, or lithium and / or metal compounds thereof (e.g., compounds of iron, manganese, nickel, copper, and / or cobalt). The electroactive material of positive electrode 24 may constitute greater than or equal to about 50%, optionally greater than or equal to about 60%, or optionally greater than or equal to about 70%, and less than or equal to about 95%, optionally less than or equal to about 90%, or optionally less than or equal to about 80% by weight of positive electrode 24.

[0096] The polymer binder is non-electrochemically active and may be included in the positive electrode 24 to provide structural integrity to the positive electrode 24 and / or to help the positive electrode 24 adhere to the main surface of the positive electrode current collector 32. Examples of polymer binders include polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber, styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), nitrile rubber (NBR), styrene-butadiene rubber (SBR), styrene-ethylene-butylene-styrene copolymer (SEBS), polyacrylates, alginates, polyacrylic acid, and combinations thereof. The polymer binder may constitute greater than or equal to about 1%, or optionally greater than or equal to about 5%, and less than or equal to about 10% by weight of the positive electrode 24.

[0097] The optional conductive material is non-electrochemically active and can be included in the positive electrode 24 to provide sufficient conductivity to the positive electrode 24 to support electron permeation therethrough. Examples of conductive materials include carbon-based materials, metals (e.g., nickel), and / or conductive polymers. Examples of conductive carbon-based materials include carbon black (CB) (e.g., acetylene black), graphite, graphene (e.g., graphene nanosheets, GNPs), graphene oxide, carbon nanotubes (CNTs), and / or carbon fibers (e.g., carbon nanofibers). Examples of conductive polymers include polyaniline, polythiophene, polyacetylene, and / or polypyrrole. When included in the positive electrode 24, the optional conductive material can constitute greater than 0%, optionally greater than or equal to about 1%, or optionally greater than or equal to about 5%, and less than or equal to about 10% by weight of the positive electrode 24.

[0098] In some aspects, the positive electrode 24 may further include particles of LiPOS. When included in the positive electrode 24, the LiPOS may constitute greater than 0%, optionally greater than or equal to about 10%, or optionally greater than or equal to about 15%, and less than or equal to about 30%, or optionally less than or equal to about 20% by weight of the positive electrode 24.

[0099] The negative electrode 22 is configured to store and release lithium ions during the charge and discharge process of the battery 20, and may be in the form of a continuous material layer disposed on the major surface of the negative electrode current collector 30. The negative electrode 22 includes an electrochemically active (electroactive) material (electroactive negative electrode material) that can store and release lithium ions by undergoing a reversible redox reaction with lithium during the charge and discharge process of the battery 20. Examples of electroactive materials for the negative electrode 22 include lithium, lithium-based materials, lithium alloys (e.g., alloys of lithium and silicon, aluminum, indium, tin, or a combination thereof), carbon-based materials (e.g., graphite, activated carbon, carbon black, hard carbon, soft carbon, and / or graphene), silicon, silicon-based materials (e.g., silicon oxide, alloys of silicon and tin, iron, aluminum, cobalt, or a combination thereof, and / or a composite material of silicon and / or silicon oxide and carbon), tin oxide, aluminum, indium, zinc, germanium, silicon oxide, lithium silicon oxide, lithium silicide, titanium oxide, lithium titanate, and a combination thereof. The electroactive material of negative electrode 22 may constitute greater than or equal to about 50%, optionally greater than or equal to about 60%, or optionally greater than or equal to about 70%, and less than or equal to about 95%, optionally less than or equal to about 90%, or optionally less than or equal to about 80% by weight of negative electrode 22.

[0100] In some aspects, the electroactive material of the negative electrode 22 may be composed of lithium, and the negative electrode 22 may be in the form of a non-porous metal film or foil, such as a lithium metal film or a lithium metal foil. In other aspects, the negative electrode 22 may be porous, and the electroactive material of the negative electrode 22 may be a granular material. In the aspect that the electroactive material of the negative electrode 22 is a granular material, the particles of the electroactive material of the negative electrode 22 may be intermixed with a polymer binder and an optional conductive material. The same polymer binder and / or conductive material disclosed above with respect to the positive electrode 24 may be used in the negative electrode 22 in substantially the same amount.

[0101] In some aspects, the negative electrode 22 may further include particles of LiPOS. When included in the negative electrode 22, the LiPOS may constitute greater than 0%, optionally greater than or equal to about 10%, or optionally greater than or equal to about 15%, and less than or equal to about 30%, or optionally less than or equal to about 20% by weight of the negative electrode 22.

[0102] The negative electrode current collector 30 and the positive electrode current collector 32 are conductive and provide electrical connections between the external circuit 36 ​​and their respective negative electrode 22 and positive electrode 24. In some aspects, the negative electrode current collector 30 and the positive electrode current collector 32 can be in the form of a non-porous metal foil, a perforated metal foil, a porous metal mesh, or a combination thereof. The negative electrode current collector 30 can be made of copper, nickel, or alloys thereof, stainless steel, or other suitable conductive materials. The positive electrode current collector 32 can be made of aluminum (Al) or other suitable conductive materials.

[0103] method

[0104] The electrolyte membrane 26 can be manufactured by preparing a precursor mixture, depositing the precursor mixture on a substrate to form a precursor layer, and then removing the solvent from the precursor layer to form an electrolyte membrane 26. The precursor mixture includes a sulfide-based solid electrolyte 46, a polymer binder 48, an inorganic filler 50, an inorganic lithium salt 52, an ionic liquid 54, an optional halide-based solid electrolyte, and an optional hydride-based solid electrolyte. The substrate may include silica glass, polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), or a combination thereof. The solvent may include a non-aqueous aprotic organic solvent. For example, the solvent may include toluene, anisole, benzene, acetonitrile, tetrahydrofuran, heptane, dimethyl carbonate, or a combination thereof. The solvent may constitute greater than or equal to about 5% and less than or equal to about 90% by weight of the precursor mixture. The precursor mixture may be deposited on a substrate, for example, by a tape casting technique using a scraper. The solvent may be removed from the precursor layer, for example, by drying the precursor layer at a temperature of about 60 degrees Celsius to evaporate the solvent therefrom. After the electrolyte membrane 26 is formed, the electrolyte membrane 26 may be removed from the substrate, for example, by peeling the electrolyte membrane 26 from the substrate. Thereafter, the electrolyte membrane 26 may be assembled into the battery 20.

[0105] In some aspects, the precursor mixture can be prepared by preparing a solution including a polymer binder 48, an inorganic filler 50, and an inorganic lithium salt 52, and then introducing the sulfide-based solid electrolyte 46 and the ionic liquid 54 into the solution. The sulfide-based solid electrolyte 46, the polymer binder 48, the inorganic filler 50, the inorganic lithium salt 52, the ionic liquid 54, the optional halide-based solid electrolyte, and the optional hydride-based solid electrolyte can be mixed together for about 2 hours to form the precursor mixture, and then the precursor mixture is deposited on a substrate.

[0106] The foregoing description is essentially only illustrative, and is by no means intended to limit the present disclosure, its application, or use. The broad teaching of the present disclosure can be implemented in various forms. Therefore, although the present disclosure includes specific examples, the true scope of the present disclosure should not be so limited, because after studying the drawings, description and appended claims, other modifications will become apparent. It should be understood that, without changing the principle of the present disclosure, one or more steps in the method can be performed in different orders (or simultaneously). In addition, although each of the embodiments is described as having certain features above, any one or more of those features described with respect to any embodiment of the present disclosure can be implemented in any other embodiment and / or combined with the features of any other embodiment, even if that combination is not explicitly described. In other words, the embodiments described are not mutually exclusive, and the replacement of one or more embodiments with each other is still within the scope of the present disclosure.

[0107] The terms used herein are only used for the purpose of describing exemplary embodiments and are not intended to be limiting. Unless the context clearly indicates otherwise, the singular forms "one", "one / a kind of" and "the" as used herein are intended to also include plural forms. The terms "include", "comprise", "contain", and "have" are inclusive, thus specifying the presence of the features, elements, compositions, steps, wholes, operations and / or components, but do not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components and / or groups thereof. Although the open-ended terms "include", "comprise", "contain", and "have" are to be understood as non-limiting terms for describing and claiming various embodiments described herein, in some aspects, the terms may be alternatively understood as more restrictive and constraining terms, such as "consisting of..." or "consisting essentially of..." Therefore, for any given embodiment of a narration composition, material, assembly, element, ingredient, feature, whole, operation and / or process step, the present disclosure also specifically includes an embodiment consisting of or essentially consisting of the compositions, materials, assemblies, elements, ingredients, features, wholes, operations and / or process steps of these narrations. In the case of “consisting of,” alternative embodiments exclude any additional compositions, materials, components, elements, ingredients, features, integers, operations and / or process steps, while in the case of “consisting essentially of,” any additional compositions, materials, components, elements, ingredients, features, integers, operations and / or process steps that materially affect the basic and novel characteristics are excluded from such embodiments, but any compositions, materials, components, elements, ingredients, features, integers, operations and / or process steps that do not materially affect the basic and novel characteristics may be included in the embodiments.

[0108] Any method steps, processes, and operations described herein should not be construed as necessarily requiring their performance in the order discussed or illustrated, unless expressly identified as an order of performance. It is also understood that additional or alternative steps may be employed unless otherwise indicated.

[0109] Although the term first, second, third etc. can be used to describe various steps, elements, components, regions, layers and / or parts in this article, these steps, elements, components, regions, layers and / or parts should not be limited by these terms unless otherwise indicated. These terms can only be used to distinguish a step, element, component, region, layer or part from another step, element, component, region, layer or part. Unless the context clearly indicates, terms such as "first", "second" and other numerical terms do not imply order or sequence when used in this article. Therefore, without departing from the teaching of exemplary embodiments, the first step, element, component, region, layer or part discussed below can be referred to as the second step, element, component, region, layer or part.

[0110] Throughout this disclosure, numerical values ​​represent approximate measurements or range limits, and encompass minor deviations from given values ​​and embodiments (those with approximately the values ​​and with the exact values). Except for the working examples provided at the end of the specific embodiments, all numerical values ​​of the parameters (e.g., quantities or conditions) in this specification should be understood to be modified by the term "about" in all cases, regardless of whether "about" actually appears before the numerical value. The numerical values ​​of the parameters in the attached claims should be understood to be modified by such terms only when the term "about" appears before the numerical value. "About" means that the numerical value allows some slight imprecision (somewhat close to precision in numerical value; approximately or reasonably close to the numerical value; almost). If the imprecision provided by "about" cannot be understood separately in this art with this common meaning, then the "about" used herein at least represents the changes that may be caused by the common methods of measuring and using such parameters. For example, "about" can include less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to 0.5%, and in some aspects, optionally less than or equal to 0.1%. In addition, the disclosure of ranges includes the disclosure of all values ​​within the entire range and further divided ranges, including endpoints and subranges given for the range.

[0111] As used herein, the terms "composition" and "material" are used interchangeably to refer broadly to a substance containing at least a preferred chemical constituent, element, or compound, but which may also contain additional elements, compounds, or substances, including trace amounts of impurities, unless otherwise indicated. An "X-based" composition or material broadly refers to a composition or material in which "X" is the single largest component of the composition or material by weight percentage (%). This can include compositions or materials having greater than 50% X by weight, as well as those having less than 50% X by weight, as long as X is the single largest component of the composition or material based on its total weight. When a composition or material is referred to as being "substantially free" of a substance, the composition or material may contain less than 5%, optionally less than 3%, optionally less than 1%, or optionally less than 0.1% of the substance by weight.

[0112] As used herein, the term "metal" may refer to a pure elemental metal or an alloy of an elemental metal with one or more other metals or nonmetallic elements (referred to as "alloying" elements). Alloying elements may be selected to impart certain desired properties to the alloy that are not exhibited by the base metal element.

Claims

1. A battery for circulating lithium ions, the battery comprising: a negative electrode comprising an electroactive negative electrode material; a positive electrode spaced apart from the negative electrode and comprising an electroactive positive electrode material; as well as An electrolyte membrane disposed between the negative electrode and the positive electrode, which provides a medium for lithium ion conduction between the negative electrode and the positive electrode, the electrolyte membrane comprising: A sulfide-based solid electrolyte comprising lithium sulfide (Li2S) and at least one element selected from phosphorus (P), tin (Sn), silicon (Si), germanium (Ge), boron (B), gallium (Ga) and aluminum (Al); polymer binders; Inorganic fillers; Inorganic lithium salts; as well as An ionic liquid comprising substantially equimolar amounts of cations and anions, the cations comprising lithium (Li + ) and ethylene glycol dimethyl ether, an imidazolium ion, a piperidinium ion, a pyrrolidinium ion, an ammonium ion, a phosphonium ion or a combination thereof, and the anion includes an arsenate ion, a phosphate ion, a sulfonimide ion, a borate ion, a chlorate ion or a combination thereof.

2. The battery according to claim 1, wherein the cations in the ionic liquid include lithium (Li + ) and triethylene glycol dimethyl ether complex; lithium (Li + ) and tetraethylene glycol dimethyl ether complex; 1-ethyl-3-methylimidazolium; 1-propyl-3-methylimidazolium; 1-butyl-3-methylimidazolium; 1,2-dimethyl-3-butylimidazolium; 1-alkyl-3-methylimidazolium, 1-allyl-3-methylimidazolium; 1,3-diallylimidazolium; 1-allyl-3-vinylimidazolium; 1-vinyl-3-ethylimidazolium; 1-cyanomethyl-3-methylimidazolium; 1,3-dicyanomethyl-imidazolium; 1-propyl-1-methylpiperidinium; 1-butyl-1-methylpiperidinium ; 1-methyl-1-ethylpyrrolidinium; 1-propyl-1-methylpyrrolidinium; 1-butyl-1-methylpyrrolidinium; methyl-methylcarboxymethyl-pyrrolidinium; tetramethylammonium; tetraethylammonium; tributylmethylammonium; diallyldimethylammonium; N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium; N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium; trimethylisobutylphosphonium; triisobutylmethylphosphonium; tributylmethylphosphonium; diethylmethylisobutylphosphonium; trihexyldecylphosphonium; trihexyltetradecylphosphonium; or a combination thereof.

3. The battery according to claim 1, wherein the anions in the ionic liquid include hexafluoroarsenate, hexafluorophosphate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, perchlorate, tetrafluoroborate, cyclo-difluoromethane-1,1-bis(sulfonyl)imide, bis(perfluoroethanesulfonyl)imide, bis(oxalato)borate, difluorooxalatoborate, bis(fluoromalonato)borate, or a combination thereof.

4. The battery according to claim 1, wherein the ionic liquid further comprises a diluent selected from the group consisting of dimethyl carbonate, ethylene carbonate, ethyl acetate, acetone, acetonitrile, toluene, propylene carbonate, diethyl carbonate, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, and combinations thereof.

5. The battery of claim 1 , wherein the sulfide-based solid electrolyte comprises lithium sulfide (Li2S) and at least one additional inorganic compound selected from phosphorus sulfide (P2S5), tin sulfide (SnS2), silicon sulfide (SiS2), germanium sulfide (GeS2), boron sulfide (B2S3), gallium sulfide (Ga2S3), aluminum sulfide (Al2S3), lithium oxide (Li2O), phosphorus oxide (P2O5), lithium fluoride (LiF), lithium chloride (LiCl), lithium bromide (LiBr), lithium iodide (LiI), arsenic sulfide (As2S5) and manganese sulfide (MnS).

6. The battery according to claim 1, wherein the polymer binder comprises polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (HNBR), styrene-butadiene rubber (SBR), polystyrene-block-poly(ethylene-random-butylene)-block-polystyrene (SEBS), or a combination thereof.

7. The battery according to claim 1, wherein the inorganic filler comprises alumina (Al2O3), silicon dioxide (SiO2), or a combination thereof.

8. The battery according to claim 1, wherein the inorganic lithium salt comprises lithium bis(trifluoromethanesulfonyl)imide (LiN(CF3SO2)2), lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2) (LiFSI) or a combination thereof.

9. The battery of claim 1, wherein the sulfide-based solid electrolyte comprises lithium phosphosulfuryl chloride (Li6PS5Cl), the polymer binder comprises polyethylene oxide, the inorganic filler comprises alumina, the inorganic lithium salt comprises lithium bis(fluorosulfonyl)imide, and the ionic liquid comprises substantially equimolar amounts of (i) lithium (Li + ) complex with tetraethylene glycol dimethyl ether and (ii) bis(trifluoromethanesulfonyl)imide.

10. The battery of claim 1, wherein the electrolyte membrane has a thickness of greater than or equal to about 5 microns and less than or equal to about 500 microns.

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