CN116969432B - Inorganic super-ion conductor material, preparation method and application thereof, inorganic solid electrolyte membrane and lithium battery - Google Patents
Inorganic super-ion conductor material, preparation method and application thereof, inorganic solid electrolyte membrane and lithium battery Download PDFInfo
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- CN116969432B CN116969432B CN202311175020.8A CN202311175020A CN116969432B CN 116969432 B CN116969432 B CN 116969432B CN 202311175020 A CN202311175020 A CN 202311175020A CN 116969432 B CN116969432 B CN 116969432B
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- ions
- lithium
- solid electrolyte
- conductor material
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- 239000000463 material Substances 0.000 title claims abstract description 81
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 61
- 229910003480 inorganic solid Inorganic materials 0.000 title claims abstract description 44
- 239000010416 ion conductor Substances 0.000 title claims abstract description 38
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 36
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 36
- 150000002500 ions Chemical class 0.000 claims abstract description 22
- 239000002226 superionic conductor Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 17
- 150000001450 anions Chemical class 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 24
- 229910021645 metal ion Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 18
- 229910001416 lithium ion Inorganic materials 0.000 claims description 18
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 18
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 18
- -1 aluminum ions Chemical class 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000002070 nanowire Substances 0.000 claims description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001424 calcium ion Inorganic materials 0.000 claims description 9
- 239000011775 sodium fluoride Substances 0.000 claims description 9
- 235000013024 sodium fluoride Nutrition 0.000 claims description 9
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 229910001430 chromium ion Inorganic materials 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- 239000002064 nanoplatelet Substances 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 235000011147 magnesium chloride Nutrition 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 235000004279 alanine Nutrition 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910001422 barium ion Inorganic materials 0.000 claims description 2
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000020 calcium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 235000013922 glutamic acid Nutrition 0.000 claims description 2
- 239000004220 glutamic acid Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 claims 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000002000 Electrolyte additive Substances 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000013543 active substance Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 15
- 210000004027 cell Anatomy 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 13
- 238000011056 performance test Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 230000002441 reversible effect Effects 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 8
- 210000000988 bone and bone Anatomy 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000010532 solid phase synthesis reaction Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000003828 vacuum filtration Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- HMPRYWSTSPTPFI-UHFFFAOYSA-N [Li].[F] Chemical compound [Li].[F] HMPRYWSTSPTPFI-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The invention relates to the technical field of secondary batteries, and discloses an inorganic super-ion conductor material, a preparation method and application thereof, an inorganic solid electrolyte membrane and a lithium battery. The inorganic super-ion conductor material comprises hydroxyapatite and doped ions doped in the hydroxyapatite; wherein the doping ions are selected from at least one of metal cations and nonmetal anions. The invention also discloses a preparation method and application of the inorganic super-ion conductor material, an inorganic solid electrolyte membrane and a lithium battery. The inorganic super-ionic conductor material obtained by the invention has the advantages of high ionic conductivity, high mechanical strength, high flame retardance and the like, can be applied to lithium batteries and other secondary batteries, can be directly used as an inorganic solid electrolyte, can be added into a polymer matrix as an inorganic active filler to be used as a composite solid electrolyte, can be added into a positive electrode and a negative electrode to be used as a lithium-conducting active substance, can be used as an electrolyte additive, a diaphragm and the like, and can be applied to various components of the battery.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to an inorganic super-ion conductor material, a preparation method and application thereof, an inorganic solid electrolyte membrane and a lithium battery.
Background
Lithium ion batteries have been widely used since commercialization, and have become an indispensable energy storage device for human life. However, with the great development of new energy devices such as portable electronic devices and new energy automobiles, the energy density and the power density of lithium batteries are more highly required.
At present, most commercial lithium ion batteries adopt graphite based on intercalation reaction, have good cycle life, but have the problem of lower capacity, and cannot meet the requirement of further development of the lithium ion batteries to higher fields such as new energy automobiles, aerospace and the like. Lithium metal is the best choice for the negative electrode of the future energy storage system due to its ultra-high theoretical specific capacity (3830 mAh g -1) and extremely low reduction potential (-3.04V vs. standard hydrogen electrode). Secondary batteries with lithium metal as the negative electrode have high specific energy (> 500Wh kg -1) and high energy density (> 1500Wh L -1). However, the adoption of the volatile and combustible electrolyte can continuously generate side reaction with the metal lithium, so that the electrolyte and the metal lithium are consumed, and a great potential safety hazard exists when lithium dendrites are formed.
In order to effectively solve the problems, the solid electrolyte is used for replacing the traditional electrolyte, so that the safety and the thermal stability of the battery are relieved, meanwhile, the lithium metal can be used as a negative electrode of the battery, and the aim of further improving the energy density is fulfilled.
The solid electrolyte is classified into an inorganic solid electrolyte, a polymer solid electrolyte and a composite solid electrolyte. The inorganic solid electrolyte has high ionic conductivity and high mechanical strength, but has interface contact problem with the electrode; the polymer solid electrolyte has high flexibility, good interface contact with the electrode and low ionic conductivity; the composite solid electrolyte combines the advantages of inorganic and polymer solid electrolytes, while having high ionic conductivity, high mechanical strength, high flexibility and good interfacial contact with the electrodes.
There is a need in the art to develop a material having high ionic conductivity, high mechanical strength, and high flame retardancy.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provides an inorganic super-ion conductor material, a preparation method and application thereof, an inorganic solid electrolyte membrane and a lithium battery.
In order to achieve the above object, a first aspect of the present invention provides an inorganic super ion conductor material, wherein the inorganic super ion conductor material comprises hydroxyapatite and a doping ion doped in the hydroxyapatite; wherein the doping ions are selected from at least one of metal cations and nonmetal anions.
A second aspect of the present invention provides a method for producing an inorganic superconducting ion conductor material according to the first aspect, the method being selected from one of a hydrothermal method, a solid phase method, and a solution stirring method.
In a third aspect, the present invention provides an inorganic super-ionic conductor material prepared by the preparation method according to the second aspect.
A fourth aspect of the present invention provides the use of the inorganic super-ionic conductor material according to the first or third aspect for the preparation of lithium batteries and other secondary batteries.
A fifth aspect of the present invention provides an inorganic solid electrolyte membrane made of the inorganic super ion conductor material according to the first or third aspect.
A sixth aspect of the invention provides a lithium battery comprising the inorganic solid electrolyte membrane of the fifth aspect.
Through the technical scheme, the beneficial technical effects obtained by the invention are as follows:
(1) The inorganic super ion conductor material provided by the invention is prepared by doping ions in hydroxyapatite, replacing part of calcium ions in the hydroxyapatite with lithium ions, magnesium ions, zinc ions, sodium ions, potassium ions, chromium ions and the like, converting the calcium ions into active fillers capable of guiding lithium, and adding a lithium ion transmission channel in the material; and replacing part of hydroxyl ions with fluoride ions, chloride ions, bromide ions, carbonate ions and the like to promote dissociation of lithium salt, and adding a lithium ion transmission channel on the surface of the material.
(2) The invention can not only independently synthesize the hydroxyapatite, but also extract the hydroxyapatite from bones or directly use the commercial product of the hydroxyapatite, and prepares the anion-cation co-doped hydroxyapatite with the morphology of nano particles, nano wires, nano sheets and the like as an inorganic super-ion conductor material by regulating and controlling the conditions of a preparation method, synthesis time, synthesis temperature and the like.
(3) The nanowire structure with the ultrahigh length-diameter ratio synthesized by the hydrothermal method can greatly improve the ionic conductivity, has high mechanical strength and high flame retardance, and can effectively inhibit the safety problems of lithium dendrite growth, thermal runaway and the like. When the electrolyte is used as an inorganic solid electrolyte, the electrolyte has a high electrochemical window and high ionic conductivity under optimal conditions, the assembled symmetrical battery can be stably circulated for 1500-2000 hours, the overpotential is stabilized below 100mV, and the solid electrolyte has excellent ion transmission capacity, and the assembled full battery has high specific capacity, excellent circulation stability and rate capability.
(4) The inorganic super-ion conductor material provided by the invention can be applied to lithium batteries and other secondary batteries, and can be used as a composite solid electrolyte filler, an anode additive, an cathode additive, an electrolyte additive, a diaphragm and the like to be applied to all components of the batteries. The preparation method is simple and controllable, the preparation process is environment-friendly and low in price, and provides a new idea for large-scale preparation and application of the inorganic super-ionic conductor material with low cost, reproducibility and high performance.
Drawings
FIG. 1 is a scanning electron microscope image of an inorganic super-ionic conductor material prepared in example 1 of the present invention;
FIG. 2 is a transmission electron microscope image of the inorganic super ion conductor material prepared in example 1 of the present invention;
FIG. 3 is a stress-strain curve of an inorganic solid electrolyte membrane prepared in example 1 of the present invention;
FIG. 4 is a linear sweep voltammogram of an inorganic solid electrolyte membrane prepared in example 1 of the present invention;
FIG. 5 is an Arrhenius graph of an inorganic solid electrolyte membrane prepared in example 1 of the present invention;
FIG. 6 is a cycle performance chart of an inorganic solid electrolyte membrane-assembled symmetrical cell prepared in example 1 of the present invention;
FIG. 7 is a graph showing the rate performance of the assembled full cell of the inorganic solid electrolyte membrane prepared in example 1 of the present invention at 0.1, 0.2, 0.3, 0.4, 0.5, 1C step current;
Fig. 8 is a graph showing the cycle performance of the assembled full cell of the inorganic solid electrolyte membrane prepared in example 1 of the present invention at a current density of 0.2C.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides an inorganic super-ion conductor material, wherein the inorganic super-ion conductor material comprises hydroxyapatite and doped ions doped in the hydroxyapatite;
Wherein the doping ions are selected from at least one of metal cations and nonmetal anions.
The hydroxyapatite with the general formula of Ca 10(PO4)6(OH)2 is a main inorganic component of the bones and teeth of vertebrates, and has good biocompatibility, flame retardance and ion exchange capability.
The invention utilizes the strong ion exchange property of the hydroxyapatite, and adds two lithium ion transmission channels in the material and on the surface by doping at least one of metal cations and nonmetal anions in the hydroxyapatite, thereby greatly improving the ion conductivity.
The invention utilizes the strong ion exchange capability of hydroxyapatite to replace part of calcium ions into metal ions such as lithium ions, sodium ions, potassium ions, magnesium ions, zinc ions and the like, and adds a lithium ion transmission channel into the material to convert inert filler into active filler; and replacing part of hydroxyl ions with anions such as fluoride ions, chloride ions, bromide ions, carbonate ions and the like, and adding a lithium ion transmission channel on the surface of the material to prepare the novel inorganic super-ion conductor material with double channels of internal and surface lithium ion transmission. The inorganic super-ion conductor material can be applied to lithium batteries and other secondary batteries, can be directly used as an inorganic solid electrolyte, has high specific capacity, good cycle stability and rate capability, and can be added into a polymer matrix as an active filler to be applied to various components of the battery, such as a composite solid electrolyte, an anode and cathode additive, an electrolyte additive, a diaphragm and the like.
In some embodiments of the invention, the metal cation is selected from at least one of lithium ion, sodium ion, potassium ion, magnesium ion, zinc ion, chromium ion, aluminum ion, barium ion, chromium ion, lead ion, and mercury ion, preferably lithium ion.
In some embodiments of the invention, the nonmetallic anion is selected from at least one of fluoride, chloride, bromide, carbonate, and sulfate, preferably fluoride.
In some embodiments of the invention, the dopant ions include metal cations and non-metal anions, preferably lithium ions and fluoride ions.
In some embodiments of the invention, the molar ratio of calcium ions to metal cations in the hydroxyapatite is in the range of from 2 to 10, preferably from 5 to 7.5.
In some embodiments of the invention, the molar ratio of metal cations to non-metal anions in the dopant ions is in the range of 0.5 to 3, preferably 0.86 to 1.23.
In some embodiments of the invention, the morphology of the inorganic super-ionic conductor material is selected from one of nanoparticles, nanowires, and nanoplatelets.
In some embodiments of the invention, the nanoparticles have an average particle size of 20 to 800nm, preferably 40 to 100nm.
In some embodiments of the invention, the aspect ratio of the nanowires is 100-50000:1, preferably 40000-50000:1.
In some embodiments of the invention, the nanoplatelets have a size of 500nm to 5 μm, preferably 500nm to 2 μm; the thickness is 20-1000nm, preferably 200-500nm.
A second aspect of the present invention provides a method for producing an inorganic superconducting ion conductor material according to the first aspect, the method being selected from one of a hydrothermal method, a solid phase method, and a solution stirring method.
According to the invention, through a hydrothermal method, a solid phase method or a solution stirring method, metal cations and nonmetal anions are selected to replace calcium ions and hydroxyl groups in the hydroxyapatite, so that the inorganic super-ion conductor material with high ion conductivity, high mechanical strength and high flame retardance is obtained. The inorganic super-ion conductor material utilizes the strong ion exchange effect of the hydroxyapatite, and calcium ions and metal ions are exchanged to enable the inert non-lithium-conducting material to be converted into an active material capable of conducting lithium, and an ion rapid transmission channel is newly added on the surface of the hydroxyapatite through hydroxyl ions and non-metal anions, so that rapid transmission of ions in the material and on the surface is realized, high ion conductivity is achieved, and rapid transmission of lithium ions is ensured.
In some embodiments of the invention, the hydrothermal process comprises the steps of:
(1) Firstly mixing a calcium source, a dispersing agent and water to obtain a mixed solution;
(2) Adjusting the pH of the mixed solution to 5-11, and adding a soluble metal ion salt solution and a phosphorus source into the mixed solution to carry out second mixing to obtain a precursor solution;
(3) Carrying out microwave hydrothermal reaction on the precursor solution, cooling a reaction product, washing and dispersing the reaction product into water;
(4) And (3) adding anion salt into the product obtained in the step (3) for third mixing, and carrying out suction filtration, washing and drying to obtain the inorganic super-ion conductor material.
The washing can be water washing and alcohol washing, and can be performed in a centrifugal mode.
In some embodiments of the invention, the solid phase method comprises the steps of:
(1') mixing and calcining hydroxyapatite powder with metal ion salt powder;
(2 ') soaking the powder obtained after the calcination in the step (1') in water;
and (3 ') carrying out suction filtration, washing and drying on the product soaked in the step (2') to obtain the inorganic super-ion conductor material.
The washing may be selected from water washing.
In some embodiments of the invention, the solution agitation method comprises the steps of:
(1 ") mixing hydroxyapatite powder with a soluble metal ion salt solution;
and (2 ') carrying out suction filtration, washing and drying on the mixed solution obtained in the step (1') to obtain the inorganic super-ion conductor material.
The washing may be selected from water washing.
In some embodiments of the invention, in the hydrothermal process, the calcium source in step (1) is selected from at least one of anhydrous calcium chloride, calcium carbonate, calcium bicarbonate, and calcium nitrate.
In some embodiments of the invention, the dispersant is selected from at least one of sodium oleate, glutamic acid, and alanine.
In some embodiments of the invention, the calcium source is used in an amount of 0.113 to 0.444g and the dispersant is used in an amount of 2 to 5g relative to 40 to 100mL of solvent.
In some embodiments of the invention, the first mixing time is 30min to 4 hours, preferably 1 to 2 hours.
In some embodiments of the invention, in step (1), the calcium source and the dispersant are separately dissolved in water to form a solution, and then the first mixing is performed.
In some embodiments of the invention, the calcium source is used in an amount of 0.113 to 0.444g relative to 20 to 50mL of water.
In some embodiments of the invention, the dispersant is used in an amount of 2 to 5g relative to 20 to 50mL of water.
In some embodiments of the invention, the pH in step (2) is 10.
In some embodiments of the present invention, the soluble metal ion salt in the soluble metal ion salt solution is selected from at least one of lithium nitrate, lithium sulfate, lithium chloride, magnesium nitrate, magnesium chloride, zinc nitrate, zinc chloride, copper nitrate, copper chloride, chromium chloride, and nickel sulfate, preferably lithium nitrate.
In some embodiments of the invention, the phosphorus source is selected from at least one of sodium dihydrogen phosphate, sodium hydrogen phosphate, calcium hydrogen phosphate, and calcium phosphate, preferably sodium dihydrogen phosphate.
In some embodiments of the invention, the molar ratio of the calcium source to the soluble metal ion salt in the soluble metal ion salt solution is from 2 to 10, preferably from 5 to 7.5, calculated as metal ion and calcium ion, respectively.
In some embodiments of the invention, the phosphorus source is used in an amount of 0.4 to 0.7g, preferably 0.55 to 0.68g, relative to 0.133g of soluble metal ion salt.
In some embodiments of the invention, the second mixing time is 30min to 4 hours, preferably 1 to 2 hours.
In some embodiments of the invention, the conditions of the microwave hydrothermal reaction of step (3) include: the reaction temperature is 100-500 ℃, preferably 100-300 ℃; the reaction time is 1 to 12 hours, preferably 2 to 6 hours.
In some embodiments of the invention, the non-metal anionic salt is selected from at least one of sodium fluoride, sodium carbonate, sodium chloride, ammonium fluoride and sodium bromide, preferably sodium fluoride.
In some embodiments of the invention, the non-metal anionic salt is used in an amount of 0.05 to 0.4g, preferably 0.1 to 0.2g, relative to 0.133g of soluble metal ion salt.
In some embodiments of the invention, the time for the third mixing is 4-24 hours, preferably 8-12 hours.
In some embodiments of the invention, the drying conditions include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 4-24 hours, preferably 12-16 hours.
The inorganic super-ion conductor material taking the hydroxyapatite as a matrix is prepared by a hydrothermal method, so that the amount of metal cations and/or nonmetallic anions doped in the inorganic super-ion conductor material can be accurately regulated and controlled, and materials with different microcosmic morphologies can be obtained.
The anion-cation co-doped hydroxyapatite prepared by a hydrothermal method is an ultra-long nanowire structure with an ultra-high length-diameter ratio, and is interwoven to form a continuous and stable ion transmission network structure, and meanwhile, the anion-cation co-doped hydroxyapatite has high ion conductivity and mechanical strength; the hydroxyapatite has excellent flame retardant property and can improve the safety of the material.
In some embodiments of the present invention, the hydroxyapatite powder is selected from at least one of commercial spherical or needle-shaped hydroxyapatite and hydroxyapatite extracted from bovine bone, porcine bone, sheep bone, fish scales, crab shell in the solid phase method and the solution agitation method.
In some embodiments of the invention, the metal ion salt powder is selected from at least one of lithium fluoride, lithium nitrate, lithium sulfate, lithium chloride, sodium fluoride, sodium carbonate, sodium sulfate, sodium nitrate, sodium bromide, potassium carbonate, potassium chloride, potassium bromide, potassium fluoride, potassium nitrate, magnesium sulfate, magnesium chloride, magnesium carbonate, zinc nitrate, zinc sulfate, zinc chloride, and ammonium chloride, preferably lithium fluoride.
In some embodiments of the present invention, the soluble metal ion salt in the soluble metal ion salt solution is selected from at least one of lithium fluoride, lithium nitrate, lithium sulfate, lithium chloride, sodium fluoride, sodium carbonate, sodium sulfate, sodium nitrate, sodium bromide, potassium carbonate, potassium chloride, potassium bromide, potassium fluoride, potassium nitrate, magnesium sulfate, magnesium chloride, zinc nitrate, zinc sulfate, zinc chloride, ammonium chloride, copper nitrate, and copper chloride, preferably lithium fluoride.
In some embodiments of the invention, the mass ratio of the hydroxyapatite powder to the metal ion salt powder in step (1') is from 10:1 to 1:50, preferably 1:4.8.
In some embodiments of the invention, the conditions of the calcination include: the calcination temperature is 200-1200 ℃, preferably 600-900 ℃; the calcination time is 1 to 10 hours, preferably 3 to 8 hours.
In some embodiments of the invention, the soaking time in step (2') is 4-24 hours, preferably 12 hours.
In some embodiments of the invention, the drying conditions of step (3') comprise: the drying temperature is 20-80deg.C, preferably 60deg.C; the drying time is 6 to 24 hours, preferably 24 hours.
In some embodiments of the invention, the mass ratio of the hydroxyapatite powder in step (1 ") to the soluble metal ion salt in the soluble metal ion salt solution is in the range of 10:1 to 1:20, preferably 1:9.5.
In some embodiments of the invention, the mixing conditions of step (1') comprise: the mixing temperature is 20-150deg.C, preferably 20-60deg.C; the mixing time is 1 to 24 hours, preferably 6 to 12 hours.
In some embodiments of the invention, the drying conditions of step (2 ") comprise: the drying temperature is 20-100deg.C, preferably 60 ℃; the drying time is 6 to 24 hours, preferably 24 hours.
The invention can not only synthesize the hydroxyapatite autonomously, but also extract the hydroxyapatite from bones or directly use the commercial products of the hydroxyapatite, and prepares the anionic-cationic co-doped hydroxyapatite with the shapes of nano particles, nano wires, nano sheets and the like by regulating and controlling the conditions of a preparation method, synthesis time, synthesis temperature and the like. The nanowire structure with the ultrahigh length-diameter ratio prepared by the hydrothermal method can greatly improve the ionic conductivity, has high mechanical strength and high flame retardance, has the advantages of high specific capacity, long cycle life, high safety and the like when used as a battery assembled by inorganic solid electrolyte, and can be used as a composite solid electrolyte filler, an anode additive, an cathode additive, an electrolyte additive, a diaphragm and the like to be applied to various components of the battery.
In a third aspect, the present invention provides an inorganic super-ionic conductor material prepared by the preparation method according to the second aspect.
A fourth aspect of the present invention provides the use of the inorganic super-ionic conductor material according to the first or third aspect for the preparation of lithium batteries and other secondary batteries; preferably, the inorganic super-ion conductor material is applied to the preparation of inorganic solid electrolyte, composite solid electrolyte, anode and cathode materials, diaphragms and electrolyte.
The inorganic super-ionic conductor material obtained by the invention has the advantages of high ionic conductivity, high mechanical strength, high flame retardance and the like, can be directly used as an inorganic solid electrolyte, can also be used as an inorganic active filler added into a polymer matrix to be used as a composite solid electrolyte, can be added into a positive electrode and a negative electrode to be used as a lithium-conducting active substance, can be used as an electrolyte additive, can be used as a diaphragm and the like, and can be applied to various components of a battery to improve the battery performance.
A fifth aspect of the present invention provides an inorganic solid electrolyte membrane made of the inorganic super ion conductor material according to the first or third aspect. The ionic conductivity of the inorganic solid electrolyte membrane is 1 multiplied by 10 -6-2×10-2S cm-1, the tensile strength is 0.5-15MPa, and the initial appearance is maintained after 500s of ignition.
An inorganic solid electrolyte membrane can be prepared by: dispersing the obtained inorganic super-ion conductor material in water, and preparing the inorganic solid electrolyte membrane by a vacuum filtration method.
A sixth aspect of the invention provides a lithium battery comprising the inorganic solid electrolyte membrane of the fifth aspect.
The battery assembled through the inorganic solid electrolyte membrane exhibits high specific capacity, excellent cycle stability and rate performance.
The present invention will be described in detail by examples.
The following examples and comparative examples were conducted under conventional conditions or conditions recommended by the manufacturer, where specific conditions were not noted. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.
The testing method comprises the following steps:
Mechanical properties (tensile strength) test: the tensile speed was 500mm/min, the sample was cut into dumbbell-shaped bars, clamped between clamps, and the thickness, width and length of the bar work area were input for tensile strength testing.
Ion conductivity test: the solid electrolyte membrane is clamped between two stainless steel gaskets and is connected with an electrochemical workstation for impedance test, and the frequency is 1MHz-0.1Hz.
Electrochemical performance test: the symmetrical cells and the full cells were assembled for testing analysis. The whole process of assembling the battery is in a glove box filled with argon, and the symmetrical battery assembling process is as follows: sequentially placing a negative electrode shell, a lithium sheet, a solid electrolyte membrane, a lithium sheet and a positive electrode shell, and placing the materials into a packaging machine to be pressurized to 50MPa; the full battery assembly process is as follows: sequentially placing a negative electrode shell, a lithium sheet, a solid electrolyte membrane, lithium iron phosphate and a positive electrode shell, and placing the materials into a packaging machine to be pressurized to 50MPa.
Symmetrical battery test: at a current density of 0.1mA cm -2, charging for 1 hour, discharging for 1 hour, and charging and discharging cycle.
And (3) multiplying power performance test: and (3) carrying out constant current charge and discharge test analysis on the full battery under the step current density, wherein the test conditions are as follows: the voltage range is 2.5-4.2V.
Reversible specific capacity and cycle performance test: and carrying out constant-current charge and discharge test analysis on the whole battery. The test conditions were: the voltage range is 2.5-4.2V and the current density is 0.2C.
Example 1
This example is intended to illustrate the preparation of inorganic super-ionic conductor materials by hydrothermal processes.
Weighing 0.331g of anhydrous calcium chloride, dissolving in 40mL of water, dissolving 4.8g of sodium oleate in 50mL of water, respectively stirring until the sodium oleate is dissolved, and mixing and stirring for 1h; adjusting the pH to 10, adding 50mL of solution containing 0.56g of sodium dihydrogen phosphate, mixing and stirring for 30min, adding 0.133g of lithium nitrate, and stirring for 1h to obtain a precursor solution; filling the precursor solution into a microwave hydrothermal reaction kettle, keeping the temperature at 200 ℃ for 4 hours, cooling the reaction product to room temperature, and dispersing the reaction product into water after washing with water and alcohol; and adding 0.2g of sodium fluoride into the product, stirring for 12 hours at room temperature, washing with water, filtering, and drying for 12 hours at 60 ℃ to obtain the inorganic super-ionic conductor material. The scanning electron microscope image and the transmission electron microscope image are respectively shown in fig. 1 and 2, and are nanowire structures with ultrahigh length-diameter ratio.
Dispersing the obtained inorganic super-ion conductor material in water, and preparing an inorganic solid electrolyte membrane by a vacuum filtration method for testing tensile strength and ion conductivity. The results show a tensile strength of up to 9.66MPa (fig. 3), an electrochemical window of up to 5.4V (fig. 4), and an ionic conductivity of up to 1.2 x 10 -2S cm-1 (fig. 5).
The electrochemical performance test results show that the assembled symmetrical cell can be stably cycled for 2000 hours, and the overpotential is stabilized at 50mV (FIG. 6).
The full cell was assembled for testing with reversible specific capacities at 165.2, 152.7, 143.4, 129.8, 120.1, 112.3mAh g -1 at step current densities of 0.1, 0.2, 0.3, 0.4, 0.5, 1.0C, respectively, and the specific capacities were also recoverable at a small current density back to 0.2C (fig. 7).
The cycle was stable for 500 cycles at a current density of 0.2C, with a capacity retention of 83.4% (FIG. 8).
Example 2
This example is intended to illustrate the preparation of inorganic super-ionic conductor materials by hydrothermal processes.
The operating conditions were the same as in example 1, except that no lithium nitrate was added to the precursor solution.
The resulting inorganic solid electrolyte membrane had a tensile strength of 9.89MPa and an ionic conductivity of 9.64X10 -5S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery can be stably circulated for 2000 hours, and the overpotential is stabilized at 100mV.
The full cell was assembled and tested at a current density of 0.2C, a capacity retention after 100 cycles of 77.9% and reversible specific capacities at the same step current densities of 147.8, 113.2, 87.1, 65.8, 55.1, 48.5mAh g -1, respectively.
Example 3
This example is intended to illustrate the preparation of inorganic super-ionic conductor materials by hydrothermal processes.
The operating conditions were the same as in example 1 except that no sodium fluoride was added to stir at room temperature after the microwave hydrothermal reaction was completed.
The resulting inorganic solid electrolyte membrane had a tensile strength of 9.57MPa and an ionic conductivity of 1.08X10 -4S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery can be stably circulated for 2000 hours, and the overpotential is stabilized at 80mV.
The full cell was assembled and tested at a current density of 0.2C with a capacity retention of 74.2% for 120 cycles and reversible specific capacities of 159.2, 136.9, 98.1, 78.3, 66.5, 52.8mAh g -1, respectively, at the same step current density.
Example 4
This example is intended to illustrate the preparation of inorganic super-ionic conductor materials by hydrothermal processes.
The operating conditions were the same as in example 1, except that the pH was adjusted to 11.
The resulting inorganic solid electrolyte membrane had a tensile strength of 8.27MPa and an ionic conductivity of 1.5X10 -4S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery can be stably circulated for 2000 hours, and the overpotential is stabilized at 80mV.
The full cell was assembled and tested at a current density of 0.2C, a capacity retention of 72.2% after 200 cycles, and reversible specific capacities of 136.5, 112.2, 97.6, 77.5, 63.7, 50.1mAh g -1 at the same step current density, respectively.
Comparative example 1
The operation conditions were the same as in example 1, except that lithium nitrate was not added to the hydroxyapatite precursor solution, and sodium fluoride was not added to the solution after the completion of the microwave hydrothermal reaction, and stirring was performed at room temperature.
The resulting inorganic solid electrolyte membrane had a tensile strength of 8.06MPa and an ionic conductivity of 1.0X10 -5S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery is tested, the overpotential is continuously increased, and the short circuit can occur after the cycle of 100 hours.
The full cell was assembled and tested, with a current density of 0.2C, a rapid decay of 0 for 70 cycles, and reversible specific capacities of 121.6, 108.9, 86.2, 64.6, 49.8, 36.7mAh g -1 at the same step current density, respectively.
Example 5
This example illustrates the preparation of inorganic super-ionic conductor materials by solid phase method.
126Mg of hydroxyapatite powder and 0.6g of lithium fluoride are weighed, mixed and placed in a tube furnace, inert gas is introduced, the mixture is calcined for 4 hours at 900 ℃, after the mixture is cooled to room temperature, the mixture is placed in deionized water, soaked for 12 hours, filtered and washed by suction, and dried for 24 hours at 60 ℃ to obtain the inorganic super-ion conductor material.
Dispersing the obtained inorganic super-ion conductor material in water, and preparing an inorganic solid electrolyte membrane by a vacuum filtration method for testing tensile strength and ion conductivity.
The resulting inorganic solid electrolyte membrane had a tensile strength of 3.54MPa and an ionic conductivity of 1.9X10 -4S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery can be stably circulated for 1500 hours, and the overpotential is stabilized at 70mV.
The full cell was assembled and tested at a current density of 0.2C, a capacity retention after 500 cycles of 75.2% and reversible specific capacities at the same step current densities of 147.8, 123.1, 109.7, 90.3, 86.2, 62.7mAh g -1, respectively.
Example 6
The operating conditions were the same as in example 5, except that the calcination temperature was 1000 ℃.
The resulting inorganic solid electrolyte membrane had a tensile strength of 7.22MPa and an ionic conductivity of 1.4X10 -4S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery can be stably circulated for 1500 hours, and the overpotential is stabilized at 80mV.
The full cell was assembled and tested at a current density of 0.2C, a capacity retention of 77.5% after 500 cycles, and reversible specific capacities of 136.9, 123.1, 109.7, 97.3, 89.2, 65.5mAh g -1 at the same step current density, respectively.
Example 7
This example is for illustrating the preparation of an inorganic super-ionic conductor material by a solution stirring method.
1.2G of lithium fluoride is weighed and dissolved in 60mL of deionized water, 126mg of hydroxyapatite powder is added, the mixture is stirred for 12 hours at 45 ℃, filtered and washed with water, and dried for 24 hours at 60 ℃ to obtain the inorganic super-ionic conductor material.
Dispersing the obtained inorganic super-ion conductor material in water, and preparing an inorganic solid electrolyte membrane by a vacuum filtration method for testing tensile strength and ion conductivity.
The resulting inorganic solid electrolyte membrane had a tensile strength of 5.23MPa and an ionic conductivity of 2.1X10 -4S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery can be stably circulated for 1500 hours, and the overpotential is stabilized at 60mV.
The full cell was assembled and tested with a current density of 0.2C, a 500 cycle capacity retention of 79.3% and reversible specific capacities at stepped current densities of 132.9, 113.7, 106.2, 80.1, 79.6, 55.4mAh g -1, respectively.
Example 8
The operating conditions were the same as in example 7, except that the mixing time was 8h.
The resulting inorganic solid electrolyte membrane had a tensile strength of 4.97MPa and an ionic conductivity of 1.9X10 -4S cm-1.
The electrochemical performance test result shows that the assembled symmetrical battery can be stably circulated for 1500 hours, and the overpotential is stabilized at 100mV.
The capacity retention rate was 78.5% at 500 cycles at a current density of 0.2C, and the reversible specific capacities at the stepped current densities were 136.7, 119.2, 96.6, 75.1, 63.2mAh g -1, respectively.
From the above examples, it can be seen that, by utilizing the strong ion exchange effect of hydroxyapatite, part of calcium ions are replaced by lithium ions, and part of hydroxyl ions are replaced by fluorine ions, so that rapid lithium-conducting channels can be introduced into the inside and the surface of the fiber, and the prepared nano-wire structure with ultra-high length-diameter ratio has the advantages of lithium-fluorine co-doped hydroxyapatite network structure, high ionic conductivity, high mechanical strength, high flame retardance, wide voltage window and the like, and the assembled battery has excellent rate performance and long cycle life, and has good application prospect as a solid electrolyte material.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (43)
1. An inorganic super ion conductor material, characterized in that the inorganic super ion conductor material consists of hydroxyapatite and metal cations and non-metal anions doped in the hydroxyapatite;
Wherein the molar ratio of calcium ions to metal cations in the hydroxyapatite is 1.5;
The molar ratio of the metal cations to the non-metal anions is 0.4;
The metal cations are at least one of lithium ions, sodium ions, potassium ions, magnesium ions, zinc ions, chromium ions, aluminum ions, barium ions, chromium ions, lead ions and mercury ions;
The nonmetallic anions are selected from at least one of fluoride, chloride, bromide, carbonate, and sulfate.
2. The material of claim 1, wherein the metal cation is lithium ion.
3. The material of claim 1, wherein the non-metal anion is a fluoride ion.
4. A material according to any one of claims 1-3, wherein the morphology of the inorganic super-ionic conductor material is selected from one of nanoparticles, nanowires and nanoplatelets.
5. The material of claim 4, wherein the nanoparticles have an average particle diameter of 20-800 nm.
6. The material of claim 5, wherein the nanoparticles have an average particle diameter of 40-100 nm.
7. The material of claim 4, wherein the nanowires have an aspect ratio of 100-50000:1.
8. The material of claim 7, wherein the nanowires have an aspect ratio of 40000-50000:1.
9. The material of claim 4, wherein the nanoplatelets have a size of 500 nm-5 μm; the thickness is 20-1000 nm.
10. The material of claim 9, wherein the nanoplatelets have a size of 500 nm-2 μιη; the thickness is 200-500 nm.
11. A method of preparing an inorganic superconducting material according to any one of claims 1 to 10, characterized in that the method is a hydrothermal method.
12. The preparation method according to claim 11, wherein the hydrothermal method comprises the steps of:
(1) Firstly mixing a calcium source, a dispersing agent and water to obtain a mixed solution;
(2) Adjusting the pH of the mixed solution to 5-11, and adding a soluble metal ion salt solution and a phosphorus source into the mixed solution to carry out second mixing to obtain a precursor solution;
(3) Carrying out microwave hydrothermal reaction on the precursor solution, cooling a reaction product, washing and dispersing the reaction product into water;
(4) And (3) adding non-metal anion salt into the product obtained in the step (3) for third mixing, and carrying out suction filtration, washing and drying to obtain the inorganic super-ion conductor material.
13. The production method according to claim 12, wherein in the hydrothermal method, the calcium source in step (1) is selected from at least one of anhydrous calcium chloride, calcium carbonate, calcium bicarbonate, and calcium nitrate.
14. The production method according to claim 12, wherein the dispersant is at least one selected from sodium oleate, glutamic acid and alanine.
15. The method of claim 12, wherein the amount of the calcium source is 0.113-0.444 g and the amount of the dispersant is 2-5 g relative to the solvent of 40-100 mL.
16. The method of claim 12, wherein the first mixing is for a time of 30 min-4 h.
17. The method of claim 16, wherein the first mixing is for a time period of 1-2 h.
18. The preparation method according to claim 12, wherein in the step (1), the calcium source and the dispersant are dissolved in water to form solutions, respectively, and the first mixing is performed.
19. The method of claim 12, wherein the calcium source is used in an amount of 0.113-0.444 g relative to 20-50 mL of water.
20. The method of claim 12, wherein the dispersant is used in an amount of 2 to 5g relative to 20 to 50 mL of water.
21. The process according to claim 12, wherein the pH in step (2) is 10.
22. The production method according to claim 12, wherein the soluble metal ion salt in the soluble metal ion salt solution is at least one selected from the group consisting of lithium nitrate, lithium sulfate, lithium chloride, magnesium nitrate, magnesium chloride, zinc nitrate, zinc chloride, copper nitrate, copper chloride, chromium chloride, and nickel sulfate.
23. The method of claim 22, wherein the soluble metal ion salt is lithium nitrate.
24. The production method according to claim 12, wherein the phosphorus source is at least one selected from the group consisting of sodium dihydrogen phosphate, sodium hydrogen phosphate, calcium hydrogen phosphate and calcium phosphate.
25. The method of claim 24, wherein the phosphorus source is sodium dihydrogen phosphate.
26. The method of claim 12, wherein the phosphorus source is used in an amount of 0.4 to 0.7: 0.7 g relative to the soluble metal ion salt of 0.133 g.
27. The method of claim 12, wherein the second mixing is for a time of 30 min-4 h.
28. The method of claim 27, wherein the second mixing is for a period of time ranging from 1 to 2h.
29. The method of claim 12, wherein the conditions of the microwave hydrothermal reaction of step (3) include: the reaction temperature is 100-500 ℃; the reaction time is 1-12 h.
30. The method of claim 29, wherein the conditions of the microwave hydrothermal reaction of step (3) comprise: the reaction temperature is 100-300 ℃; the reaction time is 2-6 h.
31. The method of claim 12, wherein the non-metal anion salt is selected from at least one of sodium fluoride, sodium carbonate, sodium chloride, ammonium fluoride, and sodium bromide.
32. The method of claim 31, wherein the non-metal anion salt is sodium fluoride.
33. The method of claim 12, wherein the non-metal anionic salt is used in an amount of 0.05-0.4 g relative to the soluble metal ion salt of 0.133 g.
34. The method of claim 12, wherein the third mixing is for a period of 4-24 h.
35. The method of claim 34, wherein the third mixing is for a period of 8-12 h.
36. The method of manufacturing according to claim 12, wherein the drying conditions include: the temperature is 20-100 ℃; the time is 4-24 h.
37. The method of claim 36, wherein the drying conditions comprise: the temperature is 40-80 ℃; the time is 12-16 h.
38. An inorganic superconducting material produced according to the production method of any one of claims 11 to 37.
39. Use of an inorganic super-ionic conductor material according to any one of claims 1-10 and 38 for the preparation of lithium batteries and other secondary batteries.
40. The use of claim 39, wherein the inorganic super-ionic conductor material is used in preparing inorganic solid state electrolytes, composite solid state electrolytes, positive and negative electrode materials, separators and electrolytes.
41. An inorganic solid electrolyte membrane made from the inorganic super ion conductor material of any one of claims 1 to 10 and 38.
42. The inorganic solid electrolyte membrane according to claim 41, wherein the inorganic solid electrolyte membrane has an ionic conductivity of 1 x 10 -6-2×10-2 S cm-1, a tensile strength of 0.5-15 MPa, and retains an initial morphology after ignition of 500 s.
43. A lithium battery comprising the inorganic solid electrolyte membrane of claim 41 or 42.
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