CN116093299B - Sodium ion battery anode material and preparation method and application thereof - Google Patents
Sodium ion battery anode material and preparation method and application thereof Download PDFInfo
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- CN116093299B CN116093299B CN202310333986.3A CN202310333986A CN116093299B CN 116093299 B CN116093299 B CN 116093299B CN 202310333986 A CN202310333986 A CN 202310333986A CN 116093299 B CN116093299 B CN 116093299B
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- China
- Prior art keywords
- positive electrode
- electrode material
- sodium
- carbon
- sodium ion
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 88
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 161
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 100
- 241000235342 Saccharomycetes Species 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 50
- 239000002121 nanofiber Substances 0.000 claims abstract description 50
- 238000011282 treatment Methods 0.000 claims abstract description 44
- 239000003607 modifier Substances 0.000 claims abstract description 41
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 89
- 239000011734 sodium Substances 0.000 claims description 62
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 57
- 239000010410 layer Substances 0.000 claims description 49
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 35
- 229910052708 sodium Inorganic materials 0.000 claims description 35
- 229910052759 nickel Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 125000005842 heteroatom Chemical group 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910000159 nickel phosphate Inorganic materials 0.000 claims description 11
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 claims description 11
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 10
- 235000019800 disodium phosphate Nutrition 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 claims description 8
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002109 single walled nanotube Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims description 6
- 208000005156 Dehydration Diseases 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 6
- 235000011180 diphosphates Nutrition 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229940048084 pyrophosphate Drugs 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000011247 coating layer Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- LSFRJVCYHFCAKA-UHFFFAOYSA-K sodium [hydroxy(oxido)phosphoryl] phosphate nickel(2+) Chemical compound [O-]P([O-])(=O)OP(=O)([O-])O.[Ni+2].[Na+] LSFRJVCYHFCAKA-UHFFFAOYSA-K 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- HKFSHRPNWRVLKE-UHFFFAOYSA-K sodium nickel(2+) phosphate Chemical compound [Na+].[Ni++].[O-]P([O-])([O-])=O HKFSHRPNWRVLKE-UHFFFAOYSA-K 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- CKVCFYYFFUHCDP-UHFFFAOYSA-M sodium;phosphoric acid;fluoride Chemical compound [F-].[Na+].OP(O)(O)=O CKVCFYYFFUHCDP-UHFFFAOYSA-M 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- -1 ammonium ions Chemical class 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 19
- 230000014759 maintenance of location Effects 0.000 abstract description 15
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000011777 magnesium Substances 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 39
- 239000011572 manganese Substances 0.000 description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 17
- 229910052749 magnesium Inorganic materials 0.000 description 17
- 229940091250 magnesium supplement Drugs 0.000 description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- 239000013078 crystal Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 15
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 11
- 229910001425 magnesium ion Inorganic materials 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 10
- 238000001354 calcination Methods 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 9
- 239000008103 glucose Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000011267 electrode slurry Substances 0.000 description 7
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 235000015097 nutrients Nutrition 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 239000006258 conductive agent Substances 0.000 description 5
- 238000009831 deintercalation Methods 0.000 description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 244000068988 Glycine max Species 0.000 description 4
- 235000010469 Glycine max Nutrition 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000001888 Peptone Substances 0.000 description 4
- 108010080698 Peptones Proteins 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 235000015278 beef Nutrition 0.000 description 4
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 238000012258 culturing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 4
- 229910021385 hard carbon Inorganic materials 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000019319 peptone Nutrition 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 3
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 238000007600 charging Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 229940085991 phosphate ion Drugs 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005056 compaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 2
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 229960003390 magnesium sulfate Drugs 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
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Images
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- 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
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a sodium ion battery anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Weighing each metal source according to the stoichiometric ratio of each metal ion in the anode material, and mixing with the modified saccharomycete solution and the nanofiber sol to obtain a precursor sol; (2) Carrying out heat treatment on the precursor sol, and then carrying out filament separation treatment to obtain a filament precursor sol, and carrying out dehydration and sintering treatment to obtain the carbon-coated anode material; (3) And mixing the carbon-coated positive electrode material with a phosphoric acid modifier, and performing sintering treatment to obtain the sodium ion battery positive electrode material. The positive electrode material prepared by the method has high conductivity, high ion conductivity and good stability, and can effectively improve the dynamic performance and long-term stability of the sodium ion battery containing the positive electrode material, thereby realizing the high capacity retention rate of the sodium ion battery in the long-term use process.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium ion battery positive electrode material, a preparation method and application thereof.
Background
Similar to lithium ion batteries, the performance of sodium ion batteries is related to the positive and negative electrode materials greatly. Because the specific capacity of hard carbon of the negative electrode material of the sodium ion battery can reach 350 mAh/g, the main link affecting the performance of the sodium ion battery at the present stage is the positive electrode material. Compared with lithium ions, the radius and the atomic mass of sodium ions are larger, the difficulty of intercalation and deintercalation of sodium ions in materials is larger and the speed is slow in the running process of the battery, and the damage of the morphology of the positive electrode material is easy to cause, so that the specific capacity, the service life, the safety performance and the like of the sodium ion battery are influenced. Therefore, compared with lithium ion batteries, the sodium ion batteries have poorer dynamic performance, the positive electrode material structure is unstable, and the positive electrode material undergoes a series of phase change discharge processes during chargingResulting in poor electrochemical performance. In terms of the stability of the layered transition metal oxide of the positive electrode material of the sodium ion battery, the layered transition metal oxide is easy to react with H in the preparation process 2 O and CO 2 The reaction causes an increase in alkaline substances (such as sodium hydroxide) in the positive electrode material, resulting in a change in the surface composition and structure of the material, poor stability, and deterioration of the final electrochemical properties.
Therefore, how to increase the electrochemical stability and improve the kinetic performance of the cathode material is one of the keys for developing high-performance sodium ion batteries.
Disclosure of Invention
The invention aims to solve the technical problem of providing a sodium ion battery positive electrode material, a preparation method and application thereof, and the stability, the conductivity and the ion conducting capacity of the positive electrode material are effectively improved through the introduction of a magnesium and hetero-atom doped carbon layer and a phosphoric acid modified layer and the wire separation treatment, so that the battery has high capacity retention rate in the long-term charge and discharge cycle process.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a preparation method of a positive electrode material of a sodium ion battery, which comprises the following steps:
(1) According to the positive electrode material Na t Ni x Mg y M z O 2 Weighing each metal source according to the stoichiometric ratio of each metal ion, and mixing the metal source with the modified saccharomycete solution and the nanofiber sol to obtain a precursor sol; the positive electrode material Na t Ni x Mg y M z O 2 Wherein M is one or more of iron, manganese, cobalt, zinc, scandium, aluminum, titanium and zirconium, t is more than or equal to 0.6 and less than or equal to 1.15, x+y+z=1, x is more than or equal to 0.2 and less than or equal to 0.6, and y is more than or equal to 0.01 and less than or equal to 0.16; the modified saccharomycete solution is ammonium ion and/or phosphate ion modified saccharomycete solution, and the nanofiber sol is prepared by mixing conductive nanofibers with a polymer solution;
(2) Carrying out heat treatment on the precursor sol, and then carrying out filament separation treatment to obtain a filament precursor sol, and then carrying out dehydration and primary sintering treatment to obtain the carbon-coated anode material;
(3) Mixing a carbon-coated positive electrode material with a phosphoric acid modifier, and forming a phosphoric acid modified layer on the surface of the carbon-coated positive electrode material through secondary sintering treatment to obtain the sodium ion battery positive electrode material; the phosphoric acid modifier is one or more of phosphate containing sodium and/or nickel, pyrophosphate, hydrogen phosphate and fluorinated phosphate.
Further, in the step (1), M is more preferably one or more of iron, manganese and cobalt.
Further, in step (1), the metal source includes a sodium source, a nickel source, a magnesium source, and an M source; wherein the sodium source is selected from one or more of sodium hydroxide, sodium sulfate, sodium chloride, sodium carbonate, sodium bromide, sodium phosphate and sodium nitrate; the nickel source is selected from one or more of nickel oxide, nickel nitrate, nickel formate, nickel acetate, nickel hydroxide, nickel sulfate and nickel chloride; the magnesium source is selected from one or more of magnesium nitrate, magnesium oxalate, magnesium hydroxide, magnesium formate, magnesium acetate, magnesium sulfate, magnesium chloride hexahydrate and anhydrous magnesium chloride; the M source is selected from one or more of iron, manganese, cobalt, zinc, scandium, aluminum, titanium, zirconium soluble sulfate, chloride, nitrate, acetate and formate.
In the step (1), a nickel source, a magnesium source and an M source are dissolved in a modified saccharomycete solution, then a sodium source is added and stirred to obtain a mixed solution, and then the mixed solution is mixed with nanofiber sol to obtain a precursor sol.
Further, in the step (1), the volume ratio of the modified saccharomycete solution to the nanofiber sol is 8-20: 0.3-2.5; the mass fraction of the conductive nano fibers in the nano fiber sol is 0.1-wt-0.8-wt%, and the mass fraction of the polymer is 0.2-wt-3 wt%;
the ratio of the total mass of each metal source to the mass of the solid in the modified saccharomycete solution and the mass of the solid in the nanofiber sol is 100: 0.5-12: 0.04-2, wherein the mass of solids in the modified saccharomycete solution is the total content of substances except water in the modified saccharomycete solution, the mass of solids in the nanofiber sol is the total content of substances except a solvent in the nanofiber sol, and the solvent is used for dissolving the polymer and can be water or an organic solvent.
Further, in the step (1), the preparation of the modified yeast solution includes: mixing the saccharomycete solution with a modifier, and performing micro-boiling treatment at 105-130 ℃ for 0.5-6 hours to obtain a modified saccharomycete solution; the modifier is one or more selected from ammonium oxalate, ammonium phosphate and ammonium hydrogen phosphate.
Further, the preparation of the yeast solution comprises: dissolving 5-40 g of yeast in 100 mL nutrient solution, culturing for 20 min-48 h, centrifuging, and washing with water to obtain a yeast solution for expanded culture; the nutrient solution comprises the following components in percentage by mass: 3-25 wt% of soybean peptone, 4-15 wt% of beef extract, 10-50 wt% of glucose, 1-6 wt% of dipotassium hydrogen phosphate, 0.5-5 wt% of diammonium hydrogen citrate, 0.2-3 wt% of sodium acetate and the balance of water.
Further, in the step (1), the preparation of the nanofiber sol comprises: and mixing the polymer, the nanofiber and the solvent, and heating until the polymer is dissolved to obtain the nanofiber sol.
Further, the polymer is selected from one or more of polyethylene glycol, polyacrylic acid, lithium polyacrylate, polyacrylamide, polyamide, polyimide and polyacrylate; the conductive nanofiber is selected from one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, fibrous conductive carbon black and fibrous graphene.
Further, in the step (2), the precursor sol is subjected to heat treatment at 80-150 ℃ until the solid content is 50% -95%.
Further, in the step (2), the diameter of the filament precursor sol is 5 μm to 2 mm.
Further, in the step (2), the temperature of the dehydration treatment is 75-120 ℃.
Further, in the step (2), in the step of the first sintering treatment: the sintering atmosphere is inert gas containing 1-3 vt percent of hydrogen, the heating rate is 3-20 ℃/min, the sintering temperature is 400-1000 ℃, and the sintering time is 10-32 h.
Further, in the step (3), the mass ratio of the carbon-coated positive electrode material to the phosphoric acid modifier is 100: 0.1-12; the phosphoric acid modifier is one or more selected from sodium hydrogen phosphate, sodium fluoride phosphate, sodium pyrophosphate, nickel sodium pyrophosphate, nickel phosphate and nickel sodium phosphate.
Further, in the step (3), the phosphoric acid modifier preferably contains both sodium and nickel elements, and more preferably a mixture of sodium hydrogen phosphate and nickel phosphate.
Further, in the step (3), in the step of the second sintering treatment: the sintering atmosphere is inert gas, the sintering temperature is 450-1100 ℃, and the sintering time is 5-24 hours.
Further, the inert gas is neon, argon, nitrogen or helium.
Further, in the step (3), the positive electrode material of the sodium ion battery is a material of a P2 structured layered oxide and an O3 structured layered oxide.
The invention provides a sodium ion battery positive electrode material, which comprises a positive electrode material, a carbon layer doped with hetero atoms and coated on the surface of the positive electrode material, and a phosphoric acid modified layer coated on the surface of the carbon layer; the carbon layer doped with the hetero atoms is a carbon layer doped with nitrogen or phosphorus; the phosphoric acid modified layer is obtained by sintering a phosphoric acid modifier, and the phosphoric acid modifier is one or more of sodium and/or nickel-containing phosphate, pyrophosphate, hydrogen phosphate and fluorinated phosphate.
Further, the positive electrode material is Na t Ni x Mg y M z O 2 Wherein M is selected from one or more of iron, manganese, cobalt, zinc, scandium, aluminum, titanium and zirconium, more preferably one or more of iron, manganese and cobalt; t is more preferably 0.6-1.15, and is more preferably 0.65-1.05; x+y+z=1, 0.2.ltoreq.x.ltoreq.0.6, 0.01.ltoreq.y.ltoreq.0.16, more preferably 0.02.ltoreq.y.ltoreq.0.06.
Further, the sodium ion battery positive electrode material can be prepared by the preparation method in the first aspect.
The third aspect of the invention provides a positive electrode plate, which comprises the positive electrode material of the sodium ion battery prepared by the preparation method of the first aspect, or the positive electrode material of the sodium ion battery of the second aspect.
According to a fourth aspect of the invention, there is provided a sodium ion battery comprising the positive electrode sheet of the third aspect.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is based on that the layered transition metal oxide is easy to generate structural change or phase transformation in the process of sodium ion deintercalation, and the electrochemical inactive magnesium ion is introduced into the positive electrode material, the magnesium ion has a similar electronic structure with the sodium ion, and the ionic radius of the magnesium ion is smaller, and the magnesium ion is introduced into the sodium layer to establish a stable support column so as to support the sodium layer, so that the volume change of the crystal structure caused by the sodium ion in the process of intercalation or deintercalation can be effectively slowed down, and the long-cycle stability of the positive electrode material is enhanced.
Meanwhile, the invention utilizes the electrostatic attraction effect between hydrophilic anionic groups (phosphorus-oxygen single bond, phosphorus-oxygen double bond and carboxyl) rich in the surface of the modified saccharomycete and nickel and magnesium ions to enable metal ions such as nickel and magnesium to carry out self-assembly on the surface of the saccharomycete and combine with the anionic groups on the surface, thereby regulating and controlling the growth process of crystals in the precursor sol; the precursor sol is prepared into filament precursor sol with a filament structure through filament separation treatment, the precursor can be fully calcined by utilizing the characteristic of large gaps of the filament structure, and meanwhile, the carbon material doped with hetero atoms (N, P) with a cell morphology microsphere structure formed by pyrolysis of modified saccharomycetes can form a carbon layer doped with hetero atoms on the surface of the positive electrode material in situ, so that the conductivity of the positive electrode material is effectively improved.
In addition, the carbon-coated positive electrode material is easy to react with water and carbon dioxide in the preparation process, so that the content of high-pH substances such as sodium hydroxide, sodium carbonate and the like in the positive electrode material is increased, and the electrochemical performance of the positive electrode material is influenced; according to the invention, an inert phosphoric acid modifier is introduced, and on one hand, the inert phosphoric acid modifier is neutralized with a high-pH substance (for example, sodium hydrogen phosphate can be used for neutralizing sodium hydroxide and sodium carbonate) so as to improve the electrochemical stability of the anode material; in addition, the phosphoric acid modifier after calcination treatment forms a P-containing metal layer on the surface of the positive electrode material, has a surface protection effect, and can effectively isolate water and carbon dioxide in air from directly contacting the positive electrode material, so that the stability of the positive electrode material in the air is improved, and meanwhile, the structural stability of the positive electrode material in the battery charging and discharging process is further improved; when the phosphoric acid modifier contains nickel, the introduction of nickel can further improve the ion conducting capacity of the positive electrode material, improve the dynamic performance of the positive electrode material and further inhibit the voltage attenuation of the positive electrode material.
2. The sodium ion battery positive electrode material prepared by the invention has lower powder resistance and low content of alkaline sodium, and the sodium ion battery prepared by taking the sodium ion battery positive electrode material as the positive electrode material shows high capacity retention rate in a cyclic charge-discharge experiment, and the capacity retention rate after 700 cycles is up to more than 81%.
Drawings
FIG. 1 is an SEM image of a positive electrode material of a sodium ion battery prepared in example 1;
fig. 2 is an XRD pattern of the positive electrode material of the sodium ion battery prepared in example 1 and layered oxides of P2 phase and O3 phase.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items. The term "comprising" or "comprises" as used herein means that it may include or comprise other components in addition to the components described. The term "comprising" or "comprising" as used herein may also be replaced by "being" or "consisting of" closed.
As described in the background art, the kinetics of sodium ion batteries are worse than those of lithium ion batteries, the structure of the positive electrode material is unstable, and the positive electrode material undergoes a series of phase change discharge processes during charging, resulting in poor electrochemical performance. In particular lamellar transition The metal oxide sodium ion battery positive electrode material is easy to be matched with H in the preparation process 2 O and CO 2 The reaction causes the increase of alkaline substances (such as sodium hydroxide and sodium carbonate) in the positive electrode material, causes the change of the surface composition and structure of the material, has poor stability and finally has the deterioration of electrochemical performance, thereby influencing the cycle stability of the battery.
In order to solve the technical problems, the embodiment of the invention provides a preparation method of a positive electrode material of a sodium ion battery, which comprises the following steps:
(1) According to the positive electrode material Na t Ni x Mg y M z O 2 Weighing each metal source according to the stoichiometric ratio of each metal ion, and mixing the metal source with the modified saccharomycete solution and the nanofiber sol to obtain a precursor sol; wherein, the positive electrode material Na t Ni x Mg y M z O 2 Wherein M is one or more of iron, manganese, cobalt, zinc, scandium, aluminum, titanium and zirconium, t is more than or equal to 0.6 and less than or equal to 1.15, x+y+z=1, x is more than or equal to 0.2 and less than or equal to 0.6, and y is more than or equal to 0.01 and less than or equal to 0.16; the modified saccharomycete solution is ammonium ion and/or phosphate ion modified saccharomycete solution, and the nanofiber sol is prepared by mixing conductive nanofibers with a polymer solution;
(2) Carrying out heat treatment on the precursor sol, and then carrying out filament separation treatment to obtain a filament precursor sol, and then carrying out dehydration and primary sintering treatment to obtain the carbon-coated anode material;
(3) Mixing the carbon-coated positive electrode material with a phosphoric acid modifier, and forming a phosphoric acid modified layer on the surface of the carbon-coated positive electrode material after secondary sintering treatment to obtain the sodium ion battery positive electrode material; the phosphoric acid modifier is one or more of sodium and/or nickel-containing phosphate, pyrophosphate, hydrogen phosphate and fluorinated phosphate.
In some preferred embodiments, the positive electrode material Na t Ni x Mg y M z O 2 More preferably, M is one or more of iron, manganese and cobalt; for example, the positive electrode material may be Na 0.68 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 、Na 0.62 Ni 0.52 Mg 0.07 Fe 0.16 Mn 0.25 O 2 、Na 0.8 0 Ni 0.50 Mg 0.11 Fe 0.14 Mn 0.25 O 2 、Na 0.85 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 Or Na (or) 0.95 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 。
The invention is based on that the layered transition metal oxide is easy to generate structural change or phase transformation in the process of sodium ion deintercalation, and the electrochemical inactive magnesium ion is introduced into the positive electrode material, wherein the magnesium ion and the sodium ion have similar electronic structures, but the magnesium ion has smaller ionic radius and has more positive charges, and the magnesium ion is introduced to break the ordered arrangement of the sodium ion and the holes, thereby effectively stabilizing the interlayer spacing of a sodium layer in the charge-discharge process, slowing down the volume change of the crystal structure caused by the sodium ion in the intercalation or deintercalation process, and further enhancing the long-cycle stability of the positive electrode material. The method is characterized in that the metal ions such as nickel, magnesium and the like are self-assembled on the surface of the saccharomycetes and are combined with the anionic groups on the surface by utilizing the electrostatic attraction effect between hydrophilic anionic groups (phosphorus-oxygen single bond, phosphorus-oxygen double bond and carboxyl) rich in the surface of the modified saccharomycetes and nickel and magnesium ions, so that the growth process of crystals in the precursor sol is regulated and controlled; the precursor sol is prepared into filament precursor sol with a filament structure through filament separation treatment, the precursor can be fully calcined by utilizing the characteristic of large gaps of the filament structure, and meanwhile, the carbon material doped with hetero atoms (N, P) with a cell morphology microsphere structure formed by pyrolysis of modified saccharomycetes can form a carbon layer doped with hetero atoms on the surface of the positive electrode material in situ, so that the conductivity of the positive electrode material is effectively improved.
On the basis, the invention further introduces the inert phosphoric acid modifier to carry out modification treatment on the carbon-coated positive electrode material, and the phosphoric acid modifier forms a P-containing metal layer on the surface of the positive electrode material after calcination treatment, thereby having a surface protection effect, effectively isolating water and carbon dioxide in air from direct contact with the positive electrode material, improving the stability of the positive electrode material in the air, and further improving the structural stability of the positive electrode material in the battery charging and discharging process.
In some preferred embodiments, the metal source includes a sodium source, a nickel source, a magnesium source, and an M source; wherein the sodium source is selected from one or more of sodium hydroxide, sodium sulfate, sodium chloride, sodium carbonate, sodium bromide, sodium phosphate and sodium nitrate; the nickel source is selected from one or more of nickel oxide, nickel nitrate, nickel formate, nickel acetate, nickel hydroxide, nickel sulfate and nickel chloride; the magnesium source is selected from one or more of magnesium nitrate, magnesium oxalate, magnesium hydroxide, magnesium formate, magnesium acetate, magnesium sulfate, magnesium chloride hexahydrate and anhydrous magnesium chloride; the M source is selected from one or more of iron, manganese, cobalt, zinc, scandium, aluminum, titanium, zirconium soluble sulfate, chloride, nitrate, acetate and formate.
Illustratively, when the positive electrode material is Na 0.68 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 When the metal source comprises a sodium source, a nickel source, a magnesium source, an iron source and a manganese source, wherein the sodium source can be sodium hydroxide, the nickel source can be nickel sulfate, the magnesium source can be magnesium oxalate, the iron source can be ferric sulfate, the manganese source can be manganese sulfate, and each metal source is prepared by the following steps: ni: mg: fe: mn in a molar ratio of 0.68:0.55:0.44:0.11:0.3 was weighed and mixed.
In some preferred embodiments, the nickel source and the magnesium source are dissolved in the modified saccharomycete solution together with the M source, then the sodium source is added and stirred to obtain a mixed solution, and then the mixed solution is mixed with the nanofiber sol to obtain the precursor sol.
In some preferred embodiments, the volume ratio of the modified yeast solution to the nanofiber sol is 8-20: 0.3-2.5; the mass fraction of the conductive nano fibers in the nano fiber sol is 0.1-wt-0.8-wt%, and the mass fraction of the polymer is 0.2-wt-3 wt%; the ratio of the total mass of each metal source to the mass of the solids in the modified saccharomycete solution and the mass of the solids in the nanofiber sol is 100: 0.5-12: and 0.04-2, wherein the mass of solids in the modified saccharomycete solution is the total content of substances except water in the modified saccharomycete solution, the mass of solids in the nanofiber sol is the total content of substances except a solvent in the nanofiber sol, and the solvent is used for dissolving the polymer and can be water or an organic solvent.
In some preferred embodiments, the preparation of the modified yeast solution comprises: mixing the saccharomycete solution with a modifier, and performing micro-boiling treatment at 105-130 ℃ for 0.5-6 hours to obtain a modified saccharomycete solution; the modifier is one or more selected from ammonium oxalate, ammonium phosphate and ammonium hydrogen phosphate. Modifying saccharomycete with modifier containing ammonium ion and/or phosphate ion to form N-and/or P-doped carbon material after the first calcination treatment, and the doped hetero atoms may be used as electron donor or acceptor to promote fast charge transfer and strengthen the electrochemical activity of the carbon material.
In some preferred embodiments, the preparation of the yeast solution comprises: dissolving 5-40 g of yeast in 100 mL nutrient solution, culturing for 20 min-48 h, centrifuging, and washing with water to obtain a yeast solution for expanded culture; wherein the nutrient solution comprises the following components in percentage by mass: 3-25 wt% of soybean peptone, 4-15 wt% of beef extract, 10-50 wt% of glucose, 1-6 wt% of dipotassium hydrogen phosphate, 0.5-5 wt% of diammonium hydrogen citrate, 0.2-3 wt% of sodium acetate and the balance of water.
In some preferred implementations, the preparation of the nanofiber sol includes: mixing a polymer, nanofiber and a solvent, and heating until the polymer is dissolved to obtain nanofiber sol; wherein the polymer is preferably polyethylene glycol, and the conductive nanofiber is preferably one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, fibrous conductive carbon black and fibrous graphene. By introducing conductive nanofibers into the sol, the conductivity of the sintered positive electrode material is further improved.
In some preferred embodiments, the precursor sol is heat treated at 80-150 ℃ to a solids content of 50% -95%, e.g., 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc., including but not limited to the solids content listed above.
In some preferred embodiments, the heat treated precursor sol is fed to a thread rolling machine, and the filament precursor sol is separated, and the diameter of the filament precursor sol is preferably 5 μm to 2 mm.
In some preferred embodiments, the filament precursor sol obtained after filament separation is dehydrated at 75-120 ℃ to avoid the influence of the residue of moisture on the sintering of subsequent materials; the temperature of the dehydration treatment may be 80 ℃, 90 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or the like, including but not limited to the temperature values listed above.
In some preferred embodiments, the dehydrated filament precursor sol is subjected to a first sintering process in which: the sintering atmosphere is inert gas containing 1-3 vt percent of hydrogen, the heating rate is 3-20 ℃/min, the sintering temperature is 400-1000 ℃, and the sintering time is 10-32 h; illustratively, the dehydrated filament precursor sol is heated to 820 ℃ at a heating rate of 12 ℃/min in nitrogen containing 2 vt% hydrogen, calcined for 10 h, annealed to room temperature, ball milled and sieved to obtain the carbon coated cathode material.
In some preferred embodiments, the mass ratio of the carbon-coated positive electrode material to the phosphoric acid modifier is 100:0.1-12, such as 100:1.3, 100:3.7, 100:4.5, 100:6, 100:7.5, 100:9, 100:10.2, 100:12, etc., including but not limited to the ratios listed above; wherein the phosphoric acid modifier is preferably one or more of sodium hydrogen phosphate, sodium fluoride phosphate, sodium pyrophosphate, nickel sodium pyrophosphate, nickel phosphate and nickel sodium phosphate.
In some preferred embodiments, the phosphoric acid modifier contains sodium and nickel, more preferably a mixture of sodium hydrogen phosphate and nickel phosphate, and the mass ratio of sodium hydrogen phosphate to nickel phosphate in the phosphoric acid modifier is 2-5:1, for example, 3:1, 4:1, 5:1, etc., including but not limited to the mass ratio listed above.
Taking a phosphoric acid modifier as a mixture of sodium hydrogen phosphate and nickel phosphate as an example, the carbon-coated positive electrode material is easy to react with water and carbon dioxide in the air in the preparation process to generate high-pH sodium hydroxide, sodium carbonate and the like, and the existence of the high-pH substances can influence the electrochemical performance of the positive electrode material. The introduced sodium hydrogen phosphate can be subjected to neutralization reaction with the high-pH substances, so that the electrochemical stability of the positive electrode material is improved, and meanwhile, the addition of the nickel phosphate introduces additional nickel into the positive electrode material, so that the ion conducting capacity of the positive electrode material can be further improved, the dynamic performance of the positive electrode material in the use process of the battery is improved, and the voltage attenuation is effectively inhibited.
In some preferred embodiments, in the step of the second sintering process: the sintering atmosphere is inert gas, the sintering temperature is 450-1100 ℃, and the sintering time is 5-24 hours.
In some preferred embodiments, the inert gas is neon, argon, nitrogen or helium in the first and second sintering treatments.
The embodiment of the invention also provides a sodium ion battery anode material, which comprises an anode material, a carbon layer doped with hetero atoms and coated on the surface of the anode material, and a phosphoric acid modified layer coated on the surface of the carbon layer; wherein the carbon layer doped with hetero atoms is a carbon layer doped with nitrogen or phosphorus; the phosphoric acid modified layer is obtained by sintering a phosphoric acid modifier, and the phosphoric acid modifier is one or more of sodium and/or nickel-containing phosphate, pyrophosphate, hydrogen phosphate and fluorinated phosphate.
In some preferred embodiments, the positive electrode material is Na t Ni x Mg y M z O 2 Wherein M is selected from one or more of iron, manganese, cobalt, zinc, scandium, aluminum, titanium and zirconium, more preferably one or more of iron, manganese and cobalt; t is more preferably 0.6-1.15, and is more preferably 0.65-1.05; x+y+z=1, 0.2.ltoreq.x.ltoreq.0.6, 0.01.ltoreq.y.ltoreq.0.16, more preferably 0.02.ltoreq.y.ltoreq.0.06.
In addition, the embodiment of the invention also provides a positive electrode plate, which comprises the sodium ion battery positive electrode material prepared by the preparation method or the sodium ion battery positive electrode material.
Specifically, the positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer arranged on at least one side of the current collector; the positive electrode active material layer is coated on the current collector through positive electrode slurry, and is obtained after drying and cold pressing; the positive electrode slurry comprises the positive electrode material of the sodium ion battery, a conductive agent, a binder and a solvent.
In some preferred embodiments, the positive electrode slurry is prepared from the sodium ion battery positive electrode material, a binder and a conductive agent according to the mass ratio of 80-100: 0.2-8: 1 to 5, more preferably 88 to 96: 0.5-3: 1-4.
Wherein the positive current collector can be selected to be aluminum foil; the conductive agent can be one or more of ketjen black, small-particle conductive carbon black, multi-wall carbon nanotubes, single-wall carbon nanotubes and fibrous graphene; the binder can be one or more of polyacrylic acid, polyvinylidene fluoride, carboxymethyl cellulose and styrene-butadiene latex; the solvent may be selected to be N-methylpyrrolidone (NMP).
In some preferred embodiments, the sodium ion battery cathode material, the binder (polyvinylidene fluoride, styrene-butadiene latex are mixed according to the mass ratio of 4:1) and the conductive agent (small particle conductive carbon black, single-walled carbon nano-tube according to the mass ratio of 19:1) are mixed according to the mass ratio of 95.5:1.8:2.7, dissolving the mixture in a certain amount of NMP, uniformly stirring to obtain positive electrode slurry, then coating the positive electrode slurry on a positive electrode current collector, drying and cutting into pieces to obtain a positive electrode plate.
The embodiment of the invention also provides a sodium ion battery, which comprises the positive pole piece.
Specifically, the sodium ion battery comprises a shell, a positive electrode plate, a diaphragm, a negative electrode plate and electrolyte. And stacking the positive electrode plate, the diaphragm and the negative electrode plate, forming a bare cell by lamination or winding, ultrasonically welding the electrode lug, loading the bare cell into a battery shell, drying to remove moisture, injecting electrolyte, and packaging to obtain the battery.
The negative electrode material in the negative electrode plate can be soft carbon, hard carbon or composite carbon, and the hard carbon can be obtained by pyrolysis of polyvinylidene chloride, glucose, sucrose, starch, cellulose, lignin, animal hair, cotton, phenolic resin, polyaniline, polyacrylonitrile, and the like.
The present invention will be further described with reference to specific examples and figures so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to be limiting.
In the following examples and comparative examples, "P & R" refers to a phosphoric acid modified layer formed by calcining a phosphoric acid modifier, wherein P is a phosphorus element and R is nickel and/or sodium element in the phosphoric acid modifier.
Example 1
The embodiment relates to preparation of a positive electrode material of a sodium ion battery, which comprises the following specific operations:
(1) Dissolving nickel sulfate, magnesium oxalate, ferric sulfate and manganese sulfate in a modified saccharomycete solution, stirring, adding sodium hydroxide, and stirring to obtain a saccharomycete-containing mixed solution (the solid mass of the modified saccharomycete solution is 41 g, the molar ratio of sodium, nickel, magnesium, iron and manganese ions is 0.68:0.55:0.04:0.11:0.3, and the total mass of nickel sulfate, magnesium oxalate, ferric sulfate, manganese sulfate and sodium hydroxide is 505 g); placing polyethylene glycol in a heating pot, injecting deionized water, heating at 70 ℃ until the polyethylene glycol is dissolved to obtain nanofiber sol containing 1.2 wt% of polyethylene glycol and 0.23 wt% of single-wall carbon nanotubes, injecting a saccharomycete-containing mixed solution and nanofiber sol into the heating pot according to the volume ratio of 10:0.5, and mixing and stirring to obtain precursor sol, wherein the solid mass of the nanofiber sol is 5.5 g; the preparation of the modified saccharomycete solution is as follows: dissolving 10 g yeast in 100 mL nutrient solution (soybean peptone 5 wt%, beef extract 4 wt%, glucose 12 wt%, dipotassium phosphate 2 wt%, diammonium hydrogen citrate 0.8 wt%, sodium acetate 0.7 wt%, and water in balance), culturing 24 h, centrifuging, and washing with water to obtain expanded yeast solution; then the microboiling soaking 3 h treatment is carried out on the microboiling mixed liquor of ammonia oxalate and ammonia phosphate (5.3 wt% of ammonia oxalate, 7.7 wt% of ammonia phosphate and the balance of water) at 110 ℃;
(2) Heating precursor sol to solid content of 85%, feeding into a thread rolling machine, separating filament precursor sol (diameter smaller than 0.3 and mm), feeding into a heating furnace, dewatering at 105deg.C, heating to 810 deg.C at heating rate of 12 deg.C/min under nitrogen atmosphere containing 2 vt%, calcining at high temperature of 10 h, annealing to room temperature, ball milling, and sieving to obtain Na 0.68 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 /C；
(3) Na is mixed with 0.68 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 Mixing and stirring a phosphoric acid modifier (obtained by mixing sodium hydrophosphate and nickel phosphate according to the mass ratio of 4:1) according to the mass ratio of 100:1.3, calcining 8 h under the condition of heating and controlling the temperature to 740 ℃ and nitrogen, annealing to room temperature, ball milling, washing, drying, sieving and demagnetizing to obtain the biochar-based polynary sodium ion positive electrode material Na 0.68 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 /C-1.3P&R。
Fig. 1 is a scanning electron microscope image of a biochar-based polynary sodium ion positive electrode material prepared in this example, and it can be seen from the image that the particle size of the positive electrode material prepared in this example is relatively uniform; fig. 2 shows XRD patterns of the biochar-based polynary sodium ion positive electrode material, in which (002) crystal plane peaks, (100) crystal plane peaks, (102) crystal plane peaks and (103) crystal plane peaks respectively belonging to the P2 phase are observed at about 16 °, 35 °, 36 ° and 42 °, and (003) crystal plane peaks (overlapping with (002) crystal plane peaks of the P2 phase), (105) crystal plane peaks and (107) crystal plane peaks respectively belonging to the O3 phase are observed at about 16 °, 45 ° and 53 °, wherein the intensities of the crystal plane peaks corresponding to the 2θ of 16 ° and 42 ° are strong, and the carbon crystal plane peaks, sodium hydrogen phosphate and nickel phosphate crystal plane peaks are not obvious.
Example 2
This example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 1 in that:
the molar ratio of sodium, nickel, magnesium, iron and manganese in the positive electrode material is 0.62:0.52:0.07:0.16:0.25;
mixing and stirring the mixed solution containing saccharomycetes and the nanofiber sol according to the volume ratio of 10:1.0;
the rest steps are the same, and the biological carbon-based polynary sodium ion positive electrode material Na is prepared 0.62 Ni 0.52 Mg 0.07 Fe 0.16 Mn 0.25 O 2 /C-1.3P&R。
Example 3
This example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 1 in that:
the molar ratio of sodium, nickel, magnesium, iron and manganese in the positive electrode material is 0.80:0.50:0.11:0.14:0.25;
mixing and stirring the mixed solution containing saccharomycetes and the nanofiber sol according to the volume ratio of 10:2.5;
the rest steps are the same, and the biological carbon-based polynary sodium ion positive electrode material Na is prepared 0.80 Ni 0.50 Mg 0.11 Fe 0.14 Mn 0.25 O 2 /C-1.3P&R。
Example 4
The embodiment relates to preparation of a positive electrode material of a sodium ion battery, which comprises the following specific operations:
(1) Dissolving nickel sulfate, magnesium oxalate, ferric sulfate and manganese sulfate in a modified saccharomycete solution, stirring, adding sodium hydroxide, and stirring to obtain a saccharomycete-containing mixed solution (the solid mass of the modified saccharomycete solution is 60 g, the molar ratio of sodium, nickel, magnesium, iron and manganese ions is 0.85:0.55:0.04:0.11:0.3, and the total mass of nickel sulfate, magnesium oxalate, ferric sulfate, manganese sulfate and sodium hydroxide is 743 g); placing polyethylene glycol in a heating pot, injecting deionized water, heating at 70 ℃ until the polyethylene glycol is dissolved to obtain nanofiber sol containing 2.5 wt% of polyethylene glycol and 0.45 wt% of single-wall carbon nanotubes, injecting a saccharomycete-containing mixed solution and nanofiber sol into the heating pot according to the volume ratio of 10:0.5, and mixing and stirring to obtain precursor sol, wherein the solid mass of the nanofiber sol is 8.9 g; the preparation of the modified saccharomycete solution is as follows: dissolving 20 g yeast in 100 mL nutrient solution (15 wt% of soybean peptone, 8 wt% of beef extract, 25 wt% of glucose, 4 wt% of dipotassium hydrogen phosphate, 2 wt% of diammonium hydrogen citrate, 0.9 wt% of sodium acetate and the balance of water), culturing 24 h, centrifuging, and washing with water to obtain a spread culture yeast solution; then the microboiling soaking of the microzyme solution at 120 ℃ is carried out on the mixed solution of ammonium oxalate and ammonium phosphate (5.3 wt percent of ammonium oxalate, 7.7 wt percent of ammonium phosphate and the balance of water) for 1 h treatment;
(2) Heating precursor sol to solid content of 76%, feeding into a thread rolling machine, separating to obtain filament precursor sol (diameter smaller than 0.3 mm), feeding into a heating furnace, dewatering at 105deg.C, and heating under nitrogen atmosphere containing 2 vt% hydrogen at a speed of 12 deg.C/minHeating to 880 deg.c, high temperature calcining 12-h, annealing to room temperature, ball milling and sieving to obtain Na 0.85 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 /C；
(3) Na is mixed with 0.85 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 Mixing and stirring a phosphoric acid modifier (obtained by mixing sodium hydrophosphate and nickel phosphate according to the mass ratio of 3:1) according to the mass ratio of 100:3.7, calcining 8 h under the condition of heating and controlling the temperature to 740 ℃ and nitrogen, annealing to room temperature, ball milling, washing, drying, sieving and demagnetizing to obtain the biochar-based polynary sodium ion positive electrode material Na 0.85 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 /C-3.7P&R。
Example 5
This example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 4 in that:
the molar ratio of sodium, nickel, magnesium, iron and manganese in the positive electrode material is 1.03:0.52:0.05:0.18:0.25;
mixing and stirring the mixed solution containing saccharomycetes and the nanofiber sol according to the volume ratio of 10:1.5;
the rest steps are the same, and the biological carbon-based polynary sodium ion positive electrode material Na is prepared 1.03 Ni 0.52 Mg 0.05 Fe 0.18 Mn 0.25 O 2 /C-3.7P&R。
Example 6
This example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 4 in that:
The molar ratio of sodium, nickel, magnesium, iron and manganese in the positive electrode material is 0.95:0.50:0.11:0.14:0.25;
mixing and stirring the mixed solution containing saccharomycetes and the nanofiber sol according to the volume ratio of 10:3.0;
the rest steps are the same, and the biological carbon-based polynary sodium ion positive electrode material Na is prepared 0.95 Ni 0.50 Mg 0.11 Fe 0.14 Mn 0.25 O 2 /C-3.7P&R。
Comparative example 1
This comparative example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 1 in that: the step of micro-boiling treatment of the mixed solution of ammonium oxalate and ammonium phosphate is omitted.
Comparative example 2
This comparative example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 1 in that: the yeast solution was replaced with glucose at the same concentration.
Comparative example 3
This comparative example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 1 in that: and the step of wire separation treatment is absent, and the precursor sol after the heating treatment is directly subjected to high-temperature calcination treatment.
Comparative example 4
This comparative example relates to the preparation of a positive electrode material for sodium ion batteries, which differs from example 1 in that: lacking step (3), only Na is prepared 0.68 Ni 0.55 Mg 0.04 Fe 0.11 Mn 0.3 O 2 /C。
Application and performance characterization
1. Assembly of sodium ion secondary battery
The positive electrode materials prepared in the above examples and comparative examples were used as positive electrode active materials to prepare corresponding sodium ion secondary batteries, respectively, and the specific operations were as follows:
(1) Mixing a positive electrode material, a binder (polyvinylidene fluoride and styrene-butadiene latex according to a mass ratio of 4:1) and a conductive agent (small-particle conductive carbon black and single-walled carbon nano-tubes according to a mass ratio of 19:1) according to a mass ratio of 95.5:1.8:2.7 adding the mixture into NMP solvent, mixing and stirring to prepare positive electrode slurry, coating the positive electrode slurry on a current collector to obtain a pole piece, drying, cold pressing, cutting and preparing the positive electrode pole piece;
(2) Sequentially stacking and winding a positive plate, a separation film and a negative plate (active substance is hard carbon obtained by pyrolysis of phenolic resin) to obtain a bare cell, ultrasonically welding a tab, putting the bare cell into a battery shell, drying to remove moisture, injecting electrolyte into the battery shell, and packaging to obtain the sodium ion secondary battery.
2. Performance testing
(1) Resistance and pH value measurement of positive electrode material
The positive electrode materials prepared in the above examples and comparative examples were tested for resistance and pH, and the specific procedures were as follows:
measurement of resistance: loading the positive electrode material of 10 g into a measuring sample stage, loading the jig into a pre-compaction instrument, starting the pre-compaction instrument to compact 15 s, loading the sample stage back into the powder resistivity instrument, and starting software to start testing the powder resistance;
determination of alkaline sodium content: the positive electrode materials prepared in examples and comparative examples were subjected to titration with hydrochloric acid to determine the content of alkaline sodium (sodium hydroxide, sodium carbonate), and the specific procedures were as follows: dispersing the sodium ion positive electrode material of 5 g in 20 mL deionized water, stirring and dispersing for 30 minutes, then filtering to obtain a supernatant, calculating the total content of hydrochloric acid consumed by titration to a titration end point by using methyl orange as an indicator of the titration end point, and calculating the total residual alkali content by the volume of the titration end point to obtain the content of alkaline sodium (sodium hydroxide and sodium carbonate);
Determination of pH: the pH of the positive electrode materials prepared in examples and comparative examples was measured by a pH meter, and the specific procedure was as follows: deionized water and a positive electrode material are mixed according to the mass ratio of 9:1, mixing and stirring, taking supernatant and measuring the pH value by a pH meter.
The test results are shown in table 1 below:
TABLE 1
As can be seen from Table 1, the positive electrode materials for sodium ion batteries prepared in examples 1 to 6 and comparative examples 3 and 4 have lower powder resistance, which is less than 250Ω. The powder resistance of the positive electrode materials prepared in comparative examples 1 and 2 was higher, and in particular, the powder resistance of the positive electrode material prepared in comparative example 1 was as high as 507.3 Ω, and this larger difference in resistance was presumed to be related to the carbon layer of the positive electrode material coating layer. The main difference between comparative examples 1 and 2 and example 1 is that the preparation of the carbon layer of the coating layer is that in comparative example 1, the step of micro boiling treatment of the mixed solution of oxalic acid ammonia and phosphoric acid ammonia is absent, in comparative example 2, the yeast solution is replaced by glucose with the same concentration on the basis of example 1, and the difference caused by different treatment methods is reflected on the carbon layer of the coating layer after sintering treatment. Compared with the carbon layer formed by calcining the unmodified saccharomycetes in the comparative example 1, the surface of the positive electrode material prepared in the example 1 and the comparative example 2 is coated with the carbon layer co-doped with nitrogen and phosphorus, and the doped nitrogen and phosphorus atoms can serve as electron donors or acceptors to promote rapid transfer of charges, so that the electrochemical activity of the carbon material is enhanced. Thus, example 1 and comparative example 2, which are cathode materials coated with a carbon layer co-doped with nitrogen and phosphorus, have lower powder resistance than comparative example 1.
In addition, the powder resistance of the positive electrode material prepared in comparative example 2 was 323.5 Ω, which is almost twice the powder resistance (167.5 Ω) of the positive electrode material prepared in example 1, and this result is presumed to be caused by the difference in the forces acting on metal ions between yeast and glucose. Compared with the glucose adopted in the comparative example 2, the saccharomycete adopted in the example 1 can regulate and control the growth process of crystals in the precursor sol through the electrostatic attraction between hydrophilic anionic groups and nickel and magnesium ions which are rich in the surface of the saccharomycete, and meanwhile, the conductive layer network formed on the surface of the positive electrode material after the saccharomycete is calcined is more uniform.
The sodium ion battery cathode materials prepared in comparative examples 3, 4 have lower powder resistance than the sodium ion battery cathode material prepared in example 1. The positive electrode material prepared in comparative example 3 has lower resistance, presumably because the specific surface area of the positive electrode material after the wire separation treatment is increased, and more bare surfaces which are not coated by the carbon layer exist, so that the corresponding powder resistance is higher, while the positive electrode material without the wire separation treatment has larger duty ratio of the surface coated by the carbon layer and the corresponding powder resistance is lower. The cathode material prepared in comparative example 4 was only a carbon-coated cathode material, whereas in example 1, a phosphoric acid modified layer was added on the basis of comparative example 4, and the introduction of a phosphoric acid modified layer having poor conductivity improved the powder resistance of the cathode material.
The above-mentioned wire separation treatment and the introduction of the phosphoric acid modification layer increase the resistance of the positive electrode material to some extent, but can effectively reduce the residual alkali amount and the pH value in the positive electrode material. The positive electrode material prepared in the above comparative example 4 does not contain a phosphoric acid modified layer, and the mass ratio of alkaline sodium in the positive electrode material measured by the positive electrode material is up to 0.000832 gwt%, and the corresponding pH value is 12.5, which is obviously higher than other positive electrode materials coated and modified by the phosphoric acid modified layer. The positive electrode materials prepared in comparative example 3 without the wire separation treatment were also higher in alkaline sodium content and corresponding pH value as compared with examples 1 to 6 and comparative examples 1 to 2, presumably due to insufficient neutralization of alkaline sodium in the positive electrode materials.
In conclusion, the modified saccharomycete is used for preparing the carbon layer doped with the hetero atoms on the surface of the positive electrode material, and then the modified phosphoric acid layer is coated, so that the conductivity of the positive electrode material can be effectively improved, and the content of alkaline substances in the positive electrode material can be reduced.
(2) Electrochemical performance of sodium ion secondary battery
The electrochemical performance of sodium ion secondary batteries prepared from different positive electrode materials was tested using an electrochemical workstation, and the charge-discharge cut-off voltage was 2.5-4.1. 4.1V. The capacity retention rate of the battery was tested by constant current charging to 4.1V at 0.1C and then discharging to 2.5V at 0.1C. The test results are shown in table 2 below:
TABLE 2
As can be seen from table 2, the sodium ion secondary batteries constructed using the positive electrode materials prepared in examples 1 to 6 having lower powder resistance and pH value had a capacity retention rate of more than 87% after 400 cycles and a capacity retention rate of not less than 81.2% after 700 cycles.
The sodium ion secondary battery constructed using the positive electrode material of comparative example 1 having a high powder resistance and a low pH value, compared with example 1, has a high capacity retention rate after 100 cycles, but the capacity retention rate is relatively decreased faster with the increase of the number of cycles, the capacity retention rate of the battery after 400 cycles is 86.6% unlike example 1 by 1.7%, and the difference between the capacity retention rate and example 1 increases to 2.1% when the number of cycles is increased to 700 cycles. In addition, the sodium ion secondary battery constructed using the positive electrode material prepared in comparative example 2 still had a higher capacity retention of 87.1% at 400 cycles (higher than comparative example 1 but lower than example 1), but the capacity retention was significantly reduced by 79.8 (lower than example 1 and comparative example 1) when the cycle was continued to 700 cycles, as compared with comparative example 1.
In addition, the sodium ion secondary battery constructed using the positive electrode material prepared in comparative example 3 having a low powder resistance and a high pH value, it is apparent from the results of the cycle test of the battery that the rate of decrease in the battery capacity increases with the increase in the number of cycles. In contrast, the sodium ion secondary battery constructed using the positive electrode material prepared in comparative example 4 had a capacity retention rate reduced to 87.8% at 100 cycles, which was lower than that after 400 cycles in example 1.
In summary, the modified saccharomycete solution is adopted as a carbon matrix, and the modified saccharomycete solution is subjected to high-temperature filament separation calcination, phosphoric acid modifier addition and other treatments, so that the surface performance of the positive electrode material can be effectively improved, the structural stability of the positive electrode material is improved, and the high capacity retention rate is maintained in the long-term cyclic charge and discharge process.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The preparation method of the positive electrode material of the sodium ion battery is characterized by comprising the following steps of:
(1) According to the positive electrode material Na t Ni x Mg y M z O 2 The stoichiometric ratio of each metal ion in the mixture is used for weighing each metal source and dissolving the metal source with modified saccharomycetesMixing the liquid and the nanofiber sol to obtain a precursor sol; the positive electrode material Na t Ni x Mg y M z O 2 Wherein M is one or more of iron, manganese, cobalt, zinc, scandium, aluminum, titanium and zirconium, t is more than or equal to 0.6 and less than or equal to 1.15, x+y+z=1, x is more than or equal to 0.2 and less than or equal to 0.6, and y is more than or equal to 0.01 and less than or equal to 0.16; the modified saccharomycete solution is modified saccharomycete solution modified by ammonium ions and/or phosphate ions, and the nanofiber sol is prepared by mixing conductive nanofibers with a polymer solution; the conductive nanofiber is selected from one or more of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers, fibrous conductive carbon black and fibrous graphene; the polymer is selected from one or more of polyethylene glycol, polyacrylic acid, lithium polyacrylate, polyacrylamide, polyamide, polyimide and polyacrylate;
(2) Carrying out heat treatment on the precursor sol, and then carrying out filament separation treatment to obtain a filament precursor sol, and then carrying out dehydration and primary sintering treatment to obtain the carbon-coated anode material;
(3) Mixing a carbon-coated positive electrode material with a phosphoric acid modifier, and forming a phosphoric acid modified layer on the surface of the carbon-coated positive electrode material after secondary sintering treatment to obtain the sodium ion battery positive electrode material; the phosphoric acid modifier is one or more of phosphate containing sodium and/or nickel, pyrophosphate, hydrogen phosphate and fluorinated phosphate.
2. The preparation method of claim 1, wherein in the step (1), the volume ratio of the modified saccharomycete solution to the nanofiber sol is 8-20: 0.3-2.5; the mass fraction of the conductive nano fibers in the nano fiber sol is 0.1-wt-0.8-wt%, and the mass fraction of the polymer is 0.2-wt-3 wt%;
the ratio of the total mass of each metal source to the mass of the solid in the modified saccharomycete solution and the mass of the solid in the nanofiber sol is 100: 0.5-12: and 0.04-2, wherein the mass of solids in the modified saccharomycete solution is the total content of substances except water in the modified saccharomycete solution, and the mass of solids in the nanofiber sol is the total content of substances except a solvent in the nanofiber sol.
3. The method according to claim 1, wherein in the step (1), the preparation of the modified yeast solution comprises: mixing the saccharomycete solution with a modifier, and performing micro-boiling treatment at 105-130 ℃ for 0.5-6 hours to obtain a modified saccharomycete solution; the modifier is one or more selected from ammonium oxalate, ammonium phosphate and ammonium hydrogen phosphate.
4. The preparation method of claim 1, wherein in the step (2), the precursor sol is subjected to heat treatment at 80-150 ℃ until the solid content is 50% -95%; the diameter of the filament precursor sol is 5 mu m-2 mm.
5. The preparation method according to claim 1, wherein in the step (2), the temperature of the dehydration treatment is 75-120 ℃; in the step of the first sintering treatment: the sintering atmosphere is inert gas containing 1-3 vt percent of hydrogen, the heating rate is 3-20 ℃/min, the sintering temperature is 400-1000 ℃, and the sintering time is 10-32 h.
6. The preparation method of claim 1, wherein in the step (3), the mass ratio of the carbon-coated positive electrode material to the phosphoric acid modifier is 100:0.1-12; the phosphoric acid modifier is one or more selected from sodium hydrogen phosphate, sodium fluoride phosphate, sodium pyrophosphate, nickel sodium pyrophosphate, nickel phosphate and nickel sodium phosphate.
7. The method according to claim 1, wherein in the step (3), the step of the second sintering treatment: the sintering atmosphere is inert atmosphere, the sintering temperature is 450-1100 ℃, and the sintering time is 5-24 h.
8. A positive electrode material of a sodium ion battery is characterized by comprising a positive electrode material and a coating layer, wherein the positive electrode material is coated on the positive electrode materialA carbon layer doped with hetero atoms on the surface of the material and a phosphoric acid modified layer coated on the surface of the carbon layer; the molecular formula of the positive electrode material is Na t Ni x Mg y M z O 2 Wherein M is one or more selected from iron, manganese, cobalt, zinc, scandium, aluminum, titanium and zirconium, t is more than or equal to 0.6 and less than or equal to 1.15,0.2, x is more than or equal to 0.6, y is more than or equal to 0.01 and less than or equal to 0.16, and x+y+z=1; the carbon layer doped with different atoms is a carbon layer doped with nitrogen and/or phosphorus; the phosphoric acid modified layer is obtained by sintering a phosphoric acid modifier, and the phosphoric acid modifier is one or more of sodium and/or nickel-containing phosphate, pyrophosphate, hydrogen phosphate and fluorinated phosphate.
9. The positive electrode plate is characterized by comprising the positive electrode material of the sodium ion battery prepared by the preparation method of any one of claims 1-7 or the positive electrode material of the sodium ion battery of claim 8.
10. A sodium ion battery comprising the positive electrode sheet of claim 9.
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