CN115084448B - Solid electrolyte/electrode integrated material for solid lithium battery, and preparation method and application thereof - Google Patents
Solid electrolyte/electrode integrated material for solid lithium battery, and preparation method and application thereof Download PDFInfo
- Publication number
- CN115084448B CN115084448B CN202210838397.6A CN202210838397A CN115084448B CN 115084448 B CN115084448 B CN 115084448B CN 202210838397 A CN202210838397 A CN 202210838397A CN 115084448 B CN115084448 B CN 115084448B
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- Prior art keywords
- solid electrolyte
- solid
- electrolyte
- lithium
- electrostatic spinning
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- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 78
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000007787 solid Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 71
- 239000003792 electrolyte Substances 0.000 claims abstract description 55
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 239000000835 fiber Substances 0.000 claims abstract description 35
- 238000007590 electrostatic spraying Methods 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 22
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 239000006183 anode active material Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 39
- 229910001416 lithium ion Inorganic materials 0.000 claims description 39
- 238000009987 spinning Methods 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000011888 foil Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 239000007774 positive electrode material Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 229910006210 Li1+xAlxTi2-x(PO4)3 Inorganic materials 0.000 claims description 3
- 229910006212 Li1+xAlxTi2−x(PO4)3 Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910010252 TiO3 Inorganic materials 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000002203 sulfidic glass Substances 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910010685 Li5La3M2O12 Inorganic materials 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000002921 oxetanes Chemical class 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000007870 radical polymerization initiator Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims 1
- 239000010406 cathode material Substances 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 239000005518 polymer electrolyte Substances 0.000 description 5
- 239000011858 nanopowder Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 150000003949 imides Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 1
- 229910011201 Li7P3S11 Inorganic materials 0.000 description 1
- 229910011187 Li7PS6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
- B05B5/16—Arrangements for supplying liquids or other fluent material
- B05B5/1608—Arrangements for supplying liquids or other fluent material the liquid or other fluent material being electrically conductive
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0419—Methods of deposition of the material involving spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a solid electrolyte/electrode integrated material for a solid lithium battery, a preparation method and application thereof, wherein an electrostatic spinning and electrostatic spraying are adopted, an anode active material and a conductive agent are injected on an electrostatic spinning fiber membrane to obtain a composite anode, and electrostatic spinning is continued on the composite anode to obtain a three-dimensional porous fiber membrane frame; dissolving lithium salt into a crosslinking monomer, and adding sulfide electrolyte to obtain a sulfide/polymer composite electrolyte precursor; the precursor is poured into a three-dimensional porous fibrous membrane frame after being heated and melted, and is uniformly cast, so that a solid electrolyte layer is obtained; and assembling the composite positive electrode, the solid electrolyte and the negative electrode into a battery core, sealing, heating to initiate monomer polymerization, and synthesizing the solid electrolyte/electrode integrated material in situ. The invention realizes the integrated design of the electrode and the electrolyte membrane of the solid lithium battery, and simultaneously obtains the solid lithium battery with stable mechanical property, good electrochemical/chemical stability and excellent cycle and multiplying power performance.
Description
Technical Field
The invention belongs to the technical field of solid-state lithium batteries, and particularly relates to a solid electrolyte/electrode integrated material for a solid-state lithium battery, and a preparation method and application thereof.
Background
Since commercialization of lithium ion batteries, the advantages of high specific capacity, long service period and the like are widely applied. However, the existing lithium ion battery has the problems of thermal runaway such as oxidative decomposition of electrolyte and the like in the use process, so that serious potential safety hazards are caused. The solid-state battery is an emerging technology, and adopts solid electrolyte to replace inflammable liquid organic electrolyte, so that the problems of electrolyte leakage and thermal runaway of the liquid lithium ion battery in the service process can be completely eradicated, and the use requirement of the lithium ion battery under extreme special conditions can be met. In addition, the solid electrolyte can be matched with a metal lithium cathode, so that the energy density of the battery can be greatly improved, however, the high interface impedance between the electrode and the electrolyte and discontinuous lithium ion conductive paths at the interface in the service process of the battery lead the cycle life and the multiplying power characteristic of the battery to be greatly limited.
The main challenges in obtaining high-performance solid-state lithium batteries are to construct a good interface contact between electrodes/electrolyte and a continuous and efficient lithium ion transmission path, the solid electrolyte plays a key role as a carrier for lithium ion transmission, and currently the solid electrolyte mainly comprises two main types, namely an inorganic solid electrolyte and an organic polymer electrolyte, wherein the inorganic solid electrolyte has ion conductivity (10 -3-10-2 S/cm) comparable to that of a liquid electrolyte, however, poor interface contact between the inorganic solid electrolyte and an electrode material leads to increased interface impedance, and problems of space charge layers, chemical/electrochemical instability and the like also lead to reduced cycle life of the battery. The polymer electrolyte has good flexibility, can effectively improve the interface contact problem, but the low room temperature ionic conductivity and poor mechanical strength limit the large-scale application of the polymer electrolyte.
The composite electrolyte combines the advantages of inorganic solid electrolyte and polymer electrolyte, and is always the focus of attention in the industry, and the most common preparation method is to add inorganic nano particles into polymer-based electrolyte to improve the ion conductivity of the composite electrolyte, however, inorganic fillers in the composite electrolyte are easy to agglomerate and particle fillers are not easy to form a continuous ion conductive network. How to form a rapid and continuous lithium ion transport path in a composite solid electrolyte is an important research direction for solid-state lithium batteries.
In order to solve the problem, patent discloses an electrolyte/electrode interface integrated construction process in a solid-state lithium battery, wherein a positive electrode material layer is firstly prepared, then a polymer electrolyte layer is synthesized on the positive electrode layer in situ through photoinitiation, and further the design of an integrated structure of the positive electrode electrolyte material is realized, however, the obtained electrolyte has lower ionic conductivity at 60 ℃, and the cycle performance and the multiplying power performance of the battery are also poor. The organic-inorganic composite all-solid electrolyte with a three-dimensional connecting network structure is prepared by using inorganic fast lithium ion conductors to form an ordered three-dimensional connecting network skeleton and filling polymer macromolecules and lithium salt into the three-dimensional connecting network. The obtained organic-inorganic composite electrolyte has high lithium ion conductivity, wide electrochemical window, good mechanical property and stability to lithium metal, and also has the work of taking a polyimide film as a three-dimensional framework, mixing an inorganic fast ion conductor with a polymer matrix and then pouring the mixture on the polyimide framework to obtain the three-dimensional inorganic polymer composite solid electrolyte. The composite electrolyte prepared by the method has a three-dimensional lithium ion transmission path, shows higher ionic conductivity, wider voltage window and better lithium stability, but when the composite electrolyte is matched with an electrode for use, the electrolyte is in solid-solid contact with an electrode material interface, interface stress problem can cause the interface chemical/electrochemical stability to be poor, and the cycle performance and the multiplying power performance of an all-solid-state battery to be poor, so that the application of the composite electrolyte is limited to a certain extent.
Disclosure of Invention
Aiming at the problems of low ionic conductivity, poor mechanical property, poor interface compatibility of solid electrolyte/electrode, large interface impedance, poor cycle life of the battery and the like of the conventional solid-state battery, the invention aims to provide a solid electrolyte/electrode integrated material for a solid-state lithium battery, a preparation method and application thereof, and an integrated design of the electrode and an electrolyte membrane of the solid-state lithium battery is realized, and a solid-state lithium battery with high energy density, good electrochemical/chemical stability and excellent cycle and multiplying power performance is also obtained.
The invention is realized by the following technical scheme, and the preparation method of the solid electrolyte/electrode integrated material for the solid lithium battery provided by the invention comprises the following steps:
Step 1) preparing electrostatic spinning solution and electrostatic spraying solution:
Dissolving lithium ion inorganic solid electrolyte in an organic solvent under the protection of inert atmosphere, magnetically stirring for 3-5 h, and then ultrasonically dispersing for 2-3 h to uniformly disperse the lithium ion inorganic solid electrolyte to obtain a solution A; then dissolving a polymer and lithium salt in the solution A, magnetically stirring for 24 hours until the polymer and the lithium salt are completely dissolved, and standing and defoaming to obtain an electrostatic spinning solution; the mass ratio of the lithium ion inorganic solid electrolyte to the lithium ion polymer solid electrolyte is (1-85): (15-99), and the lithium ion polymer solid electrolyte comprises the polymer and lithium salt in the step 1);
Dissolving an anode active material and a conductive agent according to the mass ratio of (1-2) in absolute ethyl alcohol to prepare anode active material suspension, wherein the suspension is electrostatic spray liquid;
step 2) preparing a composite positive electrode:
Adopting an electrostatic spinning machine to spin, placing an aluminum foil on a spinning receiver, conveying electrostatic spinning liquid to a spinneret through an injector, setting relevant parameters to perform electrostatic spinning, and obtaining an electrostatic spinning fiber membrane on the receiver attached with the aluminum foil; carrying out electrostatic spraying while electrostatic spinning, and injecting the electrostatic spraying liquid obtained in the step 1) into an electrostatic spinning fiber membrane through the electrostatic spraying; finally, a composite positive electrode is obtained on a receiver attached with aluminum foil, and the composite positive electrode comprises an electrostatic spinning fiber film, a positive electrode active material and a conductive agent which are uniformly immersed in the electrostatic spinning fiber film;
Step 3) constructing a three-dimensional porous fibrous membrane frame:
After preparing the composite anode, the electrostatic spinning is continued for 4-12 hours, and a layer of electrostatic spinning fiber film is formed on the composite anode, so that a three-dimensional porous fiber film frame is formed;
Step 4) preparing a solid electrolyte material:
Weighing lithium salt, dissolving the lithium salt into a crosslinking monomer to prepare a solution B, adding sulfide electrolyte nano particles into the solution B, stirring for 10-20 h, and adding an initiator to obtain a sulfide/polymer composite electrolyte precursor; pouring the obtained composite electrolyte precursor into the three-dimensional porous fibrous membrane frame obtained in the step 3) after heating and melting, and uniformly casting the composite electrolyte precursor in the three-dimensional porous fibrous membrane frame to obtain a solid electrolyte material;
And 5) assembling the solid electrolyte obtained in the step 2) and the negative electrode into a battery core, sealing after being put into a shell or packaged, heating for 2-24 hours at the temperature of 50-100 ℃ to initiate monomer polymerization, and synthesizing the solid electrolyte/electrode integrated material in situ.
Preferably, the lithium ion inorganic solid electrolyte in step 1) includes a lithium ion inorganic oxide electrolyte and a lithium ion inorganic halide electrolyte;
The lithium ion inorganic oxide electrolyte comprises one or more of Li1+xAlxTi2-x(PO4)3(0.1<x<0.6)、Li3xLa(2/3)-xTiO3(0.04<x<0.15)、Li5La3M2O12(M which is Ta or Nb and Li x+5La3Zr2-yAyO12, (A is at least one element of Al, ga, sc, yb, dy, ta, ti, V, Y, nb, hf, si, ge, sn, x is more than or equal to 1.4 and less than or equal to 2, and y is more than 0 and less than 1.0);
The lithium ion inorganic halide electrolyte comprises Li 3MX6, wherein M is a trivalent metal; x is Cl, br or I.
Preferably, the organic solvent in step 1) is selected from one or more of acetonitrile, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, anisole, chlorobenzene, o-dichlorobenzene, dimethyl sulfoxide, dichloromethane, chloroform, toluene, xylene, N-heptane, N-hexane, cyclohexane, ethyl acetate, ethyl propionate, butyl butyrate, dimethyl carbonate, ethanol, methanol, diethylene glycol dimethyl ether and cyclohexanone;
The polymer is selected from one or more of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinylpyrrolidone, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyethylene glycol acrylate, polydivinylsulfide and derivatives thereof.
Preferably, the lithium salt in step 1) and step 4) is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonimide, lithium difluorophosphate, lithium bisoxalato borate; the lithium salt used in step 4) is the same as or different from the lithium salt used in step 1).
Preferably, the positive electrode active material in the step 1) is selected from one or more of Nickel Cobalt Manganese (NCM) ternary materials, nickel Cobalt Aluminum (NCA) ternary materials, liFePO 4、Al2O3 @ NCM523, elemental sulfur and vulcanized polyacrylonitrile, and the conductive agent at least comprises one or more of acetylene black, carbon black and carbon nanotubes; and the mass ratio of the positive electrode active material to the conductive agent is 8 (1-2).
Preferably, the parameters of the electrospinning in step 2) are set as follows: the injection flow rate of the electrostatic spinning solution is 0.1-2.0 mL/h, the rotating speed of the yarn cylinder target is 1-600 rpm, the distance between the spinning nozzle and the receiving target is 10-20 cm, the positive voltage is 10-25 kV, and the negative voltage is-3 to-1 kV;
The electrostatic spray parameters were set as: the voltage is 0-15 kV, the receiving distance is 5-15 cm, the electrostatic spraying speed is 1-10 mL/h, the receiving time is adjusted according to the required quantity, the temperature is controlled above 40 ℃, and the receiving microspheres can change the size by adjusting parameters (such as voltage and flow rate);
the electrospinning parameters of step 3) are the same as those of step 2).
Further, the thickness of the composite positive electrode obtained in the step 2) is 1-60 μm.
Preferably, the crosslinking monomer in the step 4) is selected from one or more of acrylic ester derivatives, nitrile group-containing polymers, styrene, vinyl chloride, acrylonitrile, acrylamide, vinyl acetate, alkyl vinyl ether, alkylene oxide and oxetane derivatives;
The chemical formula of the sulfide solid electrolyte is as follows: the content of the aLi xR·bMyNz·cP2S5,
Wherein 0.ltoreq.a <100, 0.ltoreq.b <100, 0.ltoreq.c <100, x is 1 or 2, y is 1 or 2, z is 1,2 or 5, R is selected from S, cl, br or I, M is selected from Li, si, ge, P, sn or Sb, zn, B, N is selected from Cl, br, I, O, S or Se;
Preferably, the sulfide electrolyte is selected from one or more of Li7-XPS6-xMx(M＝Cl、Br、I,0≤x≤1),Li3PS4、Li7PS6、Li7P3S11、Li7P2S8X1(X1＝Cl、Br、I)、Li4XS4(X＝Sn、Ge、Si)、Li10TP2S12(T＝Sn、Ge、Si) systems.
The initiator is at least one selected from peroxide, azo and redox radical polymerization initiators, boron trifluoride, phosphorus pentafluoride, vinyl acetate, titanium tetrachloride, stannic chloride and zinc dichloride cationic polymerization initiators.
Further, the negative electrode in the step 5) is at least a graphite electrode membrane, a silicon carbon electrode membrane or a metal lithium negative electrode.
The invention also provides an application of the solid electrolyte/electrode integrated material prepared by the preparation method in preparing a solid lithium battery, and the solid electrolyte/electrode integrated material is formed at one time, shaped and deaerated to prepare the shaped solid lithium battery.
Compared with the prior art, the invention has obvious advantages and beneficial effects. By means of the technical scheme, the solid electrolyte/electrode integrated material for the solid lithium battery, the preparation method and the application thereof can achieve quite technical progress and practicality, and have wide utilization value, and the solid electrolyte/electrode integrated material has at least the following advantages:
(1) The invention provides a solid electrolyte/electrode integrated material for a solid lithium battery and a preparation method and application thereof.
(2) The invention provides a solid composite electrolyte, which is composed of a three-dimensional porous fibrous membrane frame and a composite electrolyte precursor immersed in the three-dimensional porous fibrous membrane frame, wherein the prepared solid electrolyte is communicated with a composite anode to form a three-dimensional frame structure, so that rapid lithium ion transmission at an interface can be realized, and the solid composite electrolyte has high mechanical strength and thermal stability and can remarkably inhibit the growth of lithium dendrites.
(3) The solid electrolyte/electrode integrated material prepared by the method can be applied to solid-state batteries, the polarization of the batteries is small in the charge and discharge process, the discharge capacity is high, the chemical/electrochemical stability is good, and the solid-state electrolyte/electrode integrated material can be applied to solid-state lithium batteries with high power and high energy density.
The foregoing description is only an overview of the present invention, and is intended to be implemented in accordance with the teachings of the present invention, as well as the preferred embodiments thereof, together with the following detailed description of the invention, given by way of illustration only, together with the accompanying drawings.
Drawings
Fig. 1 is a scanning electron micrograph of the composite positive electrode prepared in example 2.
Fig. 2 is a scanning electron micrograph of a cross section of the solid electrolyte/electrode integrated material prepared in example 2.
Fig. 3 is a charge and discharge curve of the solid-state lithium battery obtained in example 2 at cycle 2 and cycle 100.
Fig. 4 is an ac impedance curve of the solid-state lithium battery obtained in example 2 after 2 cycles and 100 cycles.
Fig. 5 is a graph of the rate performance of the solid-state lithium battery obtained in example 2.
Fig. 6 is a cycle performance chart of the solid-state lithium battery obtained in example 3.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments and the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The embodiments generally described and illustrated in the figures herein may be implemented in a variety of different configurations. Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention has no special limitation on the sources of all the raw materials used, can be sold in the market or self-made, has no special limitation on the purity, and can be used for preparing the conventional purity of the lithium battery.
Example 1
Step 1) preparing electrostatic spinning solution and electrostatic spraying solution:
Firstly, weighing about 3.6g of Li 6.4La3Zr1.4Ta0.6O12 oxide electrolyte nano particles under inert atmosphere, dissolving the nano particles in 8.8g of N, N-dimethylformamide, magnetically stirring the nano particles for 3 hours, and then performing ultrasonic dispersion for 2 hours to uniformly disperse the nano particles to obtain a solution A; then 0.8g of lithium bistrifluoromethylsulfonyl imide and 1.2g of polyvinylidene fluoride are weighed and dissolved in the solution A, and the solution A is magnetically stirred for 24 hours until the solution A is completely dissolved, and then the solution A is kept stand for deaeration to obtain electrostatic spinning solution; weighing 0.32g of positive electrode active material LiFePO 4 and 0.04g of conductive agent acetylene black (the mass ratio of LiFePO 4 to acetylene black is 8:1), and dissolving the materials in 8g of absolute ethyl alcohol to prepare positive electrode active material suspension, wherein the suspension is electrostatic spray liquid;
step 2) preparing a composite positive electrode:
Adopting an electrostatic spinning machine for spinning, placing aluminum foil on a spinning receiver, conveying electrostatic spinning solution to a spinneret through an injector, and setting related parameters: the injection flow rate of the electrostatic spinning solution is 0.18mL/h, the rotating speed of a yarn cylinder target is 100rpm, the distance between a spinning nozzle and a round receiving target is 10cm, the spinning temperature is 30 ℃, the positive voltage is 15kV, the negative voltage is-2.5 kV, the electrostatic spinning is carried out under the condition, and an electrostatic spinning fiber film is obtained on a receiver with aluminum foil; carrying out electrostatic spraying while electrostatic spinning, and injecting the electrostatic spraying liquid obtained in the step 1) into an electrostatic spinning fiber membrane through the electrostatic spraying; the electrostatic spraying parameter is set to be 7kV, the receiving distance is 10cm, the receiving time is 4 hours, the electrostatic spraying speed is 4.2mL/h, and the temperature is controlled above 40 ℃; finally, a composite positive electrode is obtained on a receiver attached with aluminum foil, wherein the composite positive electrode comprises an electrostatic spinning fiber film, and a positive electrode active material and a conductive agent which are uniformly immersed in the electrostatic spinning fiber film.
Step 3) constructing a three-dimensional porous fibrous membrane frame:
after preparing the composite positive electrode, electrostatic spinning is continued for 4 hours, and a layer of electrostatic spinning fiber film is formed on the composite positive electrode, so that a three-dimensional porous fiber film frame is obtained, a through lithium ion transmission channel is formed between the three-dimensional porous fiber film frame and the composite positive electrode, and the electrostatic spinning parameters in the step are consistent with those in the step 2), namely: the injection flow rate of the electrostatic spinning solution is 0.18mL/h, the rotating speed of the yarn cylinder target is 100rpm, the distance between the spinning nozzle and the round receiving target is 10cm, the spinning temperature is 30 ℃, the positive voltage is 15kV, and the negative voltage is-2.5 kV.
Step 4) preparing a solid electrolyte material:
Weighing 0.13g of lithium bistrifluoromethylsulfonyl imide as lithium salt, adding the lithium bistrifluoromethylsulfonyl imide into 1g of polyethylene glycol methyl ether acrylate monomer to prepare solution B, wherein the monomer concentration in the solution B is 1mol/mL, adding 0.3gLi 10GeP2S12 powder (Li 10GeP2S12 powder is purchased from the market) into the solution B, stirring for 10 hours, and adding 0.02g of azodiisobutyronitrile initiator to obtain a sulfide/polymer composite electrolyte precursor; and (3) pouring the obtained composite electrolyte precursor into the three-dimensional porous fibrous membrane frame obtained in the step (3) after heating and melting, and uniformly casting the composite electrolyte precursor in the three-dimensional porous fibrous membrane frame to obtain the solid electrolyte material.
And under the condition of room temperature, carrying out alternating current impedance test and mechanical property test on the prepared solid electrolyte material. In the ac impedance test, stainless steel was used as an electrode, and the results were: the lithium ion conductivity was 1.1X10 -3 S/cm and the tensile strength was 72 Mpa.
Step 5) assembling the composite anode obtained in the step 2) and the solid electrolyte material obtained in the step 4) with a graphite electrode membrane (the graphite electrode membrane is used as a negative electrode) to form a battery core, sealing after being put into a shell or bag, heating for 6 hours at the temperature of 60 ℃ at 5pa to initiate monomer polymerization, and synthesizing the solid electrolyte/electrode integrated material in situ; and then forming, shaping and degassing to obtain the LiFePO 4/graphite solid-state lithium battery.
Example 2
Step 1) preparing electrostatic spinning solution and electrostatic spraying solution:
Firstly, weighing about 3.6g of Li 1.3Al0.3Ti1.7(PO4)3 oxide electrolyte nano particles under inert atmosphere, dissolving the nano particles in 8.8g N-methyl pyrrolidone, magnetically stirring the nano particles for 3 hours, and then performing ultrasonic dispersion for 2 hours to uniformly disperse the nano particles to obtain a solution A; then 0.8g of lithium bis (oxalato) borate (LiBOB) and 1.2g of polyacrylonitrile are weighed and dissolved in the solution A, and the solution A is magnetically stirred for 24 hours until the solution is completely dissolved, and then the solution is kept stand for deaeration to obtain electrostatic spinning solution; weighing 0.32g of positive electrode active material Al 2O3 to coat NCM523 (Al 2O3 @NCM523) and 0.04g of conductive agent carbon black (the mass ratio of Al 2O3 @NCM523 to carbon black is 8:1), and dissolving the materials in 8g of absolute ethyl alcohol to prepare positive electrode active material suspension, wherein the suspension is electrostatic spray liquid;
step 2) preparing a composite positive electrode:
Adopting an electrostatic spinning machine for spinning, placing aluminum foil on a spinning receiver, conveying electrostatic spinning solution to a spinneret through an injector, and setting related parameters: the injection flow rate of the electrostatic spinning solution is 0.12mL/h, the rotating speed of a yarn cylinder target is 150rpm, the distance between a spinning nozzle and a round receiving target is 15cm, the spinning temperature is 30 ℃, the positive voltage is 15kV, the negative voltage is-2.5 kV, the electrostatic spinning is carried out under the condition, and an electrostatic spinning fiber film is obtained on a receiver with aluminum foil; carrying out electrostatic spraying while electrostatic spinning, and injecting the electrostatic spraying liquid obtained in the step 1) into an electrostatic spinning fiber membrane through the electrostatic spraying; the electrostatic spraying parameter is set to be 10kV, the receiving distance is 5cm, the receiving time is 6h, the electrostatic spraying speed is 5.1mL/h, and the temperature is controlled above 40 ℃; finally, a composite positive electrode is obtained on a receiver attached with aluminum foil, wherein the composite positive electrode comprises an electrostatic spinning fiber film, and a positive electrode active material and a conductive agent which are uniformly immersed in the electrostatic spinning fiber film.
Step 3) constructing a three-dimensional porous fibrous membrane frame:
after preparing the composite positive electrode, electrostatic spinning is continued for 8 hours, and a layer of electrostatic spinning fiber film is formed on the composite positive electrode, so that a three-dimensional porous fiber film frame is obtained, a through lithium ion transmission channel is formed between the three-dimensional porous fiber film frame and the positive electrode, and the electrostatic spinning parameters in the step are consistent with those in the step 2), namely: the injection flow rate of the electrostatic spinning solution is 0.12mL/h, the distance between the spinneret and the round receiving target is 15cm, the spinning temperature is 30 ℃, the positive voltage is 15kV, and the negative voltage is-2.5 kV.
Step 4) preparing a solid electrolyte material:
Weighing 0.13g of lithium bis (oxalato) borate (LiBOB) as lithium salt, adding the lithium bis (oxalato) borate into 1g of diethylene glycol dimethacrylate monomer to prepare a solution B, wherein the monomer concentration in the solution B is 1mol/mL, adding 0.2g of Li 6PS5 Cl nano powder (the Li 6PS5 Cl nano powder is purchased from the market) into the solution B, stirring for 10 hours, and adding 0.03g of boron trifluoride initiator to obtain a sulfide/polymer composite electrolyte precursor; and (3) pouring the obtained composite electrolyte precursor into the three-dimensional porous fibrous membrane frame obtained in the step (3) after heating and melting, and uniformly casting the composite electrolyte precursor in the three-dimensional porous fibrous membrane frame to obtain the solid electrolyte material.
And 5) assembling the composite anode prepared in the step 2) and the solid electrolyte material obtained in the step 4) with a lithium metal negative electrode into a battery core, sealing after being put into a shell or packaged, heating for 6 hours at the temperature of 2pa and 70 ℃ to initiate monomer polymerization, synthesizing a solid electrolyte/electrode integrated material in situ, then performing formation, shaping and degassing to prepare the formed Al 2O3 @NCM523/Li solid lithium battery.
And under the condition of room temperature, carrying out alternating current impedance test and mechanical property test on the prepared solid electrolyte material. In the ac impedance test, stainless steel was used as an electrode, and the results were: the lithium ion conductivity was 1.2X10 -3 S/cm and the tensile strength was 78 Mpa.
Fig. 1 is a scanning electron micrograph of the composite positive electrode obtained in this example, and it can be seen from the figure: the composite positive electrode provided by the invention consists of an electrostatic spinning fibrous membrane three-dimensional frame, an active material immersed in the electrostatic spinning fibrous membrane three-dimensional frame and a conductive agent.
Fig. 2 is a scanning electron micrograph of a cross section of the solid electrolyte/electrode integrated material prepared in this example, and it is apparent from the figure that the composite positive electrode layer and the solid electrolyte layer are separated at the interface, and the interface contact is good.
Fig. 3 shows charge and discharge curves of the solid-state lithium battery obtained in this example at the 2 nd and 100 th turns, as can be seen from the figure: the solid-state lithium battery prepared by the invention has smaller polarization and higher discharge capacity in the charge and discharge process.
Fig. 4 is an ac impedance curve of the solid-state lithium battery obtained in this example after the 2 nd and 100 th cycles, and it is clear from the graph that the solid-state lithium battery prepared in this example has small impedance change and good chemical/electrochemical stability.
Fig. 5 is a graph showing the rate performance of the solid-state lithium battery obtained in this example, and it can be seen from the graph: the solid-state lithium battery prepared by the embodiment has the characteristics of good multiplying power performance and high power.
Example 3
Step 1) preparing electrostatic spinning solution and electrostatic spraying solution:
Firstly, weighing about 3.6g of Li 7La3Zr2O12 oxide electrolyte nano particles under inert atmosphere, dissolving the nano particles in 8.8g of N, N-dimethylformamide, magnetically stirring for 5 hours, and then dispersing the nano particles by ultrasonic for 2 hours to uniformly disperse the nano particles to obtain a solution A; then 0.8g of lithium perchlorate (LiClO 4) and 1.2g of polyethylene oxide are weighed and dissolved in the solution A, and the solution A is magnetically stirred for 24 hours until the solution A is completely dissolved, and then the solution A is kept stand for deaeration to obtain electrostatic spinning solution; weighing 0.32g of anode active material, namely vulcanized polyacrylonitrile (SPAN) and 0.04g of conductive agent, namely carbon nano tube (the mass ratio of the vulcanized polyacrylonitrile to the carbon nano tube is 8:1), and dissolving the materials into 15g of absolute ethyl alcohol to prepare anode active material suspension, wherein the suspension is electrostatic spray liquid;
step 2) preparing a composite positive electrode:
Adopting an electrostatic spinning machine for spinning, placing aluminum foil on a spinning receiver, conveying electrostatic spinning solution to a spinneret through an injector, and setting related parameters: the injection flow rate of the electrostatic spinning solution is 0.15mL/h, the rotating speed of a yarn cylinder target is 200rpm, the distance between a spinning nozzle and a round receiving target is 20cm, the spinning temperature is 35 ℃, the positive voltage is 15kV, the negative voltage is-2.5 kV, the electrostatic spinning is carried out under the condition, and an electrostatic spinning fiber film is obtained on a receiver with aluminum foil; carrying out electrostatic spraying while electrostatic spinning, and injecting the electrostatic spraying liquid obtained in the step 1) into an electrostatic spinning fiber membrane through the electrostatic spraying; the electrostatic spraying parameter is set to be 10kV, the receiving distance is 15cm, the receiving time is 10h, the electrostatic spraying speed is 4.5mL/h, and the temperature is controlled above 40 ℃; finally, a composite positive electrode is obtained on a receiver attached with aluminum foil, wherein the composite positive electrode comprises an electrostatic spinning fiber film, and a positive electrode active material and a conductive agent which are uniformly immersed in the electrostatic spinning fiber film.
Step 3) constructing a three-dimensional porous fibrous membrane frame:
After preparing the composite positive electrode, electrostatic spinning is continued for 12 hours, and a layer of electrostatic spinning fiber film is formed on the composite positive electrode, so that a three-dimensional porous fiber film frame is obtained, a through lithium ion transmission channel is formed between the three-dimensional porous fiber film frame and the positive electrode, and the electrostatic spinning parameters in the step are consistent with those in the step 2), namely: the injection flow rate of the electrostatic spinning solution is 0.15mL/h, the rotating speed of the yarn cylinder target is 200rpm, the distance between the spinning nozzle and the round receiving target is 20cm, the spinning temperature is 35 ℃, the positive voltage is 15kV, and the negative voltage is-2.5 kV.
Step 4) preparing a solid electrolyte material:
Weighing 0.13g of lithium perchlorate (LiClO 4) as lithium salt, adding the lithium salt into 1g of alkyl vinyl ether monomer to prepare solution B, wherein the monomer concentration in the solution B is 1mol/mL, adding 0.3g of Li 7P3S11 nano powder (the Li 7P3S11 nano powder is purchased from the market) into the solution B, stirring for 20 hours, and adding 0.02g of vinyl acetate initiator to obtain a sulfide/polymer composite electrolyte precursor; and (3) pouring the obtained composite electrolyte precursor into the three-dimensional porous fibrous membrane frame obtained in the step (3) after heating and melting, and uniformly casting the composite electrolyte precursor in the three-dimensional porous fibrous membrane frame to obtain the solid electrolyte material.
Step 5) assembling the composite anode prepared in the step 2) and the solid electrolyte material obtained in the step 4) with a lithium metal negative electrode to form a battery core, sealing after being put into a shell or packaged, heating for 8 hours at the temperature of 75 ℃ at 1pa to initiate monomer polymerization, and synthesizing the solid electrolyte/electrode integrated material in situ; and then forming, shaping and degassing to obtain the SPAN/Li solid-state lithium battery.
And under the condition of room temperature, carrying out alternating current impedance test and mechanical property test on the prepared solid electrolyte material. In the ac impedance test, stainless steel was used as an electrode, and the results were: the lithium ion conductivity was 1.0X10 -3 S/cm, and the tensile strength was 80 Mpa.
Fig. 6 is a cycle performance chart of the solid-state lithium battery obtained in this example, and it can be seen from the chart: the solid-state lithium battery prepared by the invention can stably circulate for 200 circles, and has good circulation stability and longer circulation life.
The porous ceramic electrolyte fibrous membrane (namely the electrostatic spinning fibrous membrane) is obtained by an electrostatic spinning method, the composite positive electrode and the solid electrolyte are connected into a whole, the structural stability of the solid-state battery is ensured, a high-efficiency continuous three-dimensional lithium ion transmission channel is formed between the positive electrode and the electrolyte, the circulation stability and the multiplying power performance of the battery are improved, meanwhile, the rigid three-dimensional frame structure is also beneficial to inhibiting the growth of lithium dendrites, the three-dimensional porous fibrous membrane frame and sulfide/polymer composite electrolyte precursors in the porous ceramic electrolyte fibrous membrane frame are polymerized in situ, the interface impedance of the electrode/electrolyte is obviously reduced, and the integrated design of the electrode and the electrolyte membrane of the solid-state lithium battery is realized by the invention, and meanwhile, the solid-state lithium battery with stable structure, good electrochemical/chemical stability and excellent circulation and multiplying power performance is also obtained.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the solid electrolyte/electrode integrated material for the solid lithium battery is characterized by comprising the following steps of:
Step 1) preparing electrostatic spinning solution and electrostatic spraying solution:
Dissolving lithium ion inorganic solid electrolyte in an organic solvent under the protection of inert atmosphere, magnetically stirring for 3-5 h, and then ultrasonically dispersing for 2-3 h to uniformly disperse the lithium ion inorganic solid electrolyte to obtain a solution A; dissolving a polymer and lithium salt in the solution A, magnetically stirring for 24 hours until the polymer and the lithium salt are completely dissolved, and standing and defoaming to obtain an electrostatic spinning solution; the mass ratio of the lithium ion inorganic solid electrolyte to the lithium ion polymer solid electrolyte is (1-85): (15-99), and the lithium ion polymer solid electrolyte comprises the polymer and lithium salt in the step 1);
Dissolving an anode active material and a conductive agent according to the mass ratio of (1-2) in absolute ethyl alcohol to prepare anode active material suspension, wherein the suspension is electrostatic spray liquid;
step 2) preparing a composite positive electrode:
Adopting an electrostatic spinning machine to spin, placing an aluminum foil on a spinning receiver, conveying electrostatic spinning liquid to a spinneret through an injector, setting relevant parameters to perform electrostatic spinning, and obtaining an electrostatic spinning fiber membrane on the receiver attached with the aluminum foil; carrying out electrostatic spraying while electrostatic spinning, and injecting the electrostatic spraying liquid obtained in the step 1) into an electrostatic spinning fiber membrane through the electrostatic spraying; finally, a composite positive electrode is obtained on a receiver attached with aluminum foil, and the composite positive electrode comprises an electrostatic spinning fiber film, a positive electrode active material and a conductive agent which are uniformly immersed in the electrostatic spinning fiber film;
Step 3) constructing a three-dimensional porous fibrous membrane frame:
After preparing the composite anode, the electrostatic spinning is continued for 4-12 hours, and a layer of electrostatic spinning fiber film is formed on the composite anode, so that a three-dimensional porous fiber film frame is formed;
Step 4) preparing a solid electrolyte material:
Weighing lithium salt, dissolving the lithium salt into a crosslinking monomer to prepare a solution B, adding sulfide solid electrolyte into the solution B, stirring for 10-20 h, and adding an initiator to obtain a sulfide/polymer composite electrolyte precursor; pouring the obtained composite electrolyte precursor into the three-dimensional porous fibrous membrane frame obtained in the step 3) after heating and melting, and uniformly casting the composite electrolyte precursor in the three-dimensional porous fibrous membrane frame to obtain a solid electrolyte material;
And 5) assembling the solid electrolyte material prepared in the step 2) and the composite anode and the solid electrolyte material obtained in the step 4) with a cathode material into a battery core, sealing after being put into a shell or packaged, heating for 2-24 hours at the temperature of 50-100 ℃ for initiating monomer polymerization at the pressure of 0.1-10 pa, and synthesizing the solid electrolyte/electrode integrated material in situ.
2. The method for producing a solid electrolyte/electrode integrated material for a solid lithium battery according to claim 1, wherein the lithium ion inorganic solid electrolyte in step 1) includes a lithium ion inorganic oxide electrolyte and a lithium ion inorganic halide electrolyte;
The lithium ion inorganic oxide electrolyte comprises one or more of Li1+xAlxTi2-x(PO4)3、Li3xLa(2/3)-xTiO3、Li5La3M2O12、Lix+5La3Zr2-yAyO12;
The value range of x in Li 1+xAlxTi2-x(PO4)3 is 0.1< x <0.6; the value range of x in Li 3xLa(2/3)-xTiO3 is 0.04< x <0.15; m in Li 5La3M2O12 is Ta or Nb; a in Li x+5La3Zr2-yAyO12 is at least one element in Al, ga, sc, yb, dy, ta, ti, V, Y, nb, hf, si, ge, sn, x is more than or equal to 1.4 and less than or equal to 2, and y is more than 0 and less than 1.0;
The lithium ion inorganic halide electrolyte comprises Li 3MX6, wherein M is a trivalent metal; x is Cl, br or I.
3. The method for preparing a solid electrolyte/electrode integrated material for a solid lithium battery according to claim 1, wherein the organic solvent in step 1) is selected from one or more of acetonitrile, N-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, N-methylformamide, anisole, chlorobenzene, o-dichlorobenzene, dimethyl sulfoxide, dichloromethane, chloroform, toluene, xylene, N-heptane, N-hexane, cyclohexane, ethyl acetate, ethyl propionate, butyl butyrate, dimethyl carbonate, ethanol, methanol, diethylene glycol dimethyl ether and cyclohexanone;
The polymer is selected from one or more of polyethylene oxide, polypropylene oxide, polyacrylonitrile, polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinylpyrrolidone, polymethyl methacrylate, polyvinylidene fluoride-hexafluoropropylene, polyethylene glycol acrylate, polydivinylsulfide and derivatives thereof.
4. The method for producing a solid electrolyte/electrode integrated material for a solid lithium battery according to claim 1, wherein the lithium salt in step 1) and step 4) is one or more selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonimide, lithium difluorophosphate, lithium bisoxalato borate; the lithium salt used in step 4) is the same as or different from the lithium salt used in step 1).
5. The method for preparing a solid electrolyte/electrode integrated material for a solid lithium battery according to claim 1, wherein the positive electrode active material in step 1) is selected from one or more of a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material, liFePO 4、Al2O3 @ NCM523, elemental sulfur, and vulcanized polyacrylonitrile, and the conductive agent at least comprises one or more of acetylene black, carbon black, and carbon nanotubes; and the mass ratio of the positive electrode active material to the conductive agent is 8 (1-2).
6. The method for producing a solid electrolyte/electrode integrated material for a solid-state lithium battery according to claim 1, wherein the parameters of the electrospinning in step 2) are set as follows: the injection flow rate of the electrostatic spinning solution is 0.1-2.0 mL/h, the rotating speed of the yarn cylinder target is 1-600 rpm, the distance between the spinning nozzle and the receiving target is 10-20 cm, the positive voltage is 10-25 kV, and the negative voltage is-3 to-1 kV;
The electrostatic spray parameters were set as: the voltage is 0-15 kV, the receiving distance is 5-15 cm, the electrostatic spraying speed is 1-10 mL/h, and the temperature is controlled above 40 ℃;
the electrospinning parameters of step 3) are the same as those of step 2).
7. The method for producing a solid electrolyte/electrode integrated material for a solid lithium battery according to claim 1, wherein the thickness of the composite positive electrode obtained in step 2) is 1 to 60. Mu.m.
8. The method for preparing a solid electrolyte/electrode integrated material for a solid lithium battery according to claim 1, wherein the crosslinking monomer in the step 4) is one or more selected from the group consisting of acrylate derivatives, nitrile group-containing polymers, styrene, vinyl chloride, acrylonitrile, acrylamide, vinyl acetate, alkyl vinyl ether, alkylene oxide, and oxetane derivatives;
The chemical formula of the sulfide solid electrolyte is as follows: aLi xR·bMyNz·cP2S5, wherein 0.ltoreq.a <100, 0.ltoreq.b <100, 0.ltoreq.c <100, x is 1 or 2, y is 1 or 2, z is 1,2 or 5, R is selected from S, cl, br or I, M is selected from Li, si, ge, P, sn or Sb, zn, B, N is selected from Cl, br, I, O, S or Se;
The initiator is at least one selected from peroxide, azo and redox radical polymerization initiators, boron trifluoride, phosphorus pentafluoride, vinyl acetate, titanium tetrachloride, stannic chloride and zinc dichloride cationic polymerization initiators.
9. The method for preparing a solid electrolyte/electrode integrated material for a solid lithium battery according to claim 1, wherein the negative electrode in step 5) is at least a graphite electrode membrane, a silicon carbon electrode membrane, or a metallic lithium negative electrode.
10. Use of the solid electrolyte/electrode integrated material prepared by the preparation method of claim 1 in the preparation of a solid-state lithium battery.
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