CN117334820A - High-compaction polyanion type sodium ion battery positive electrode material and preparation method thereof - Google Patents
High-compaction polyanion type sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN117334820A CN117334820A CN202311336615.7A CN202311336615A CN117334820A CN 117334820 A CN117334820 A CN 117334820A CN 202311336615 A CN202311336615 A CN 202311336615A CN 117334820 A CN117334820 A CN 117334820A
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- compaction
- water
- preparing
- precursor
- ion battery
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- 238000005056 compaction Methods 0.000 title claims abstract description 45
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007774 positive electrode material Substances 0.000 title claims description 14
- 229920000447 polyanionic polymer Polymers 0.000 title abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 83
- 239000000843 powder Substances 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002002 slurry Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000010406 cathode material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 238000000197 pyrolysis Methods 0.000 claims description 8
- 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 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- DEUJSGDXBNTQMY-UHFFFAOYSA-N 1,2,2-trifluoroethanol Chemical compound OC(F)C(F)F DEUJSGDXBNTQMY-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229940071264 lithium citrate Drugs 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 description 45
- 239000011734 sodium Substances 0.000 description 35
- 239000000243 solution Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- 238000004080 punching Methods 0.000 description 12
- 230000002829 reductive effect Effects 0.000 description 11
- 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 description 10
- 239000010410 layer Substances 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 6
- 235000019799 monosodium phosphate Nutrition 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910000314 transition metal oxide Inorganic materials 0.000 description 3
- VHVMXWZXFBOANQ-UHFFFAOYSA-N 1-Penten-3-ol Chemical compound CCC(O)C=C VHVMXWZXFBOANQ-UHFFFAOYSA-N 0.000 description 2
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical class [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229960003351 prussian blue Drugs 0.000 description 2
- 239000013225 prussian blue Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 alcohol compound Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 235000001727 glucose Nutrition 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
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- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/381—Alkaline or alkaline earth metals elements
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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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Abstract
The invention discloses a high-compaction polyanion sodium ion battery anode material and a preparation method thereof, comprising the following steps: s1, preparing an ionic precursor solution: mixing and dissolving a water-soluble alkali metal source, a water-soluble transition metal source and an anion source to form a uniform ionic precursor solution; s2, preparing precursor powder by calcining: calcining and drying the precursor solution by adopting high-temperature cracking equipment to obtain uniform precursor powder; s3, preparing precursor slurry: mixing and stirring precursor powder, a carbon source, water and an alcohol organic solvent to form uniform precursor slurry; s4, sintering at a high temperature: and drying the precursor slurry, and then placing the dried precursor slurry in a protective atmosphere for high-temperature calcination treatment to obtain the polyanionic cathode material. The high-compaction polyanionic sodium ion battery anode material and the preparation method thereof have the characteristics of high compaction density, small specific surface area and excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a high-compaction polyanion type sodium ion battery anode material and a preparation method thereof.
Background
The positive electrode materials of sodium ion batteries are of various types, including Prussian blue and its analogues, transition metal oxides and polyanionic materials. Prussian blue and analogues thereof have higher capacity and discharge voltage, but lattice water in the structure is difficult to remove, and gas is easily generated in the charging and discharging process, so that the battery fails; the transition metal oxide has higher compaction density and higher discharge capacity, but complex phase change exists in the process of sodium intercalation and deintercalation, so that the transition metal oxide has a collapsed structure and serious performance attenuation; the polyanion compound has stable three-dimensional framework, excellent multiplying power performance and high stability, but has lower capacity and smaller compaction density, and is only suitable for the energy storage field with low energy density requirement.
Polyanionic materials are generally framework structures composed of alkali metal ions, transition metal ions, and anionic groups connected to one another in the form of co-points/planes/lines. The polyanion type material has low electronic conductivity due to the fact that the anion group in the structure is large and does not have electronic transition capability. At present, an in-situ carbon coating process is generally adopted in the market, an organic carbon source is introduced in the initial synthesis process of the material, and the surface carbon of the material is modified through high-temperature pyrolysis, so that the electronic conductivity of the material is improved. However, the mode of introducing carbon source in the initial synthesis process can prevent the growth of crystal grains in the sintering process to a certain extent, influence the crystallinity of the material and the size of material particles, lead to low compaction density of the material and influence the improvement of the energy density of a battery system.
Disclosure of Invention
The invention aims to provide a high-compaction polyanion sodium ion battery anode material and a preparation method thereof, and the high-compaction polyanion sodium ion battery anode material has the characteristics of high compaction density, small specific surface area and excellent electrochemical performance.
The invention can be realized by the following technical scheme:
the invention discloses a preparation method of a high-compaction polyanion sodium ion battery anode material, which comprises the following steps:
s1, preparing an ionic precursor solution: mixing and dissolving a water-soluble alkali metal source, a water-soluble transition metal source and an anion source to form a uniform ionic precursor solution;
s2, preparing precursor powder by calcining: calcining and drying the precursor solution by adopting high-temperature cracking equipment to obtain uniform precursor powder;
s3, preparing precursor slurry: mixing and stirring precursor powder, a carbon source, water and an alcohol organic solvent to form uniform precursor slurry;
s4, sintering at a high temperature: and drying the precursor slurry, and then placing the dried precursor slurry in a protective atmosphere for high-temperature calcination treatment to obtain the polyanionic cathode material.
Further, in step S1, the water-soluble alkali metal source is an acidic sodium/lithium salt, and the acidic sodium/lithium salt is one or more selected from sodium chloride/lithium, sodium sulfate/lithium, sodium nitrate/lithium, sodium formate, sodium acetate/lithium, and sodium citrate. In the invention, the acid salt is adopted to reduce the excessive influence on the acid-base property of the solution, and effectively avoid the precipitation of metal ions caused by the excessive alkalinity.
Further, in step S1, the water-soluble transition metal source is a transition metal-based compound and its derivative, and the transition metal-based compound and its derivative are selected from one or more of iron nitrate/cobalt/nickel/manganese, iron chloride/cobalt/nickel/manganese, iron sulfate/cobalt/nickel/manganese, and iron acetate/cobalt/nickel/manganese.
Further, in step S1, the anion source is a phosphorus-containing compound selected from one or more of phosphoric acid, dihydrogen phosphate, pyrophosphoric acid, and metaphosphoric acid.
Further, in step S2, the pyrolysis temperature is not less than 600 ℃. The elements such as chlorine, sulfur, nitrogen, ammonia and the like can be decomposed and volatilized in the form of gaseous oxides at a higher high-temperature pyrolysis temperature, residual ions are fused and bonded, and are solidified into spherical compact particles after cooling, and finally, the particles are in a crystalline state of only retaining sodium/lithium elements, transition metal elements and phosphate radical/pyrophosphate radical, so that the high-temperature pyrolysis temperature cracking device has higher compaction density.
Further, in the step S3, the carbon source is an organic water-soluble carbon source, and the addition amount of the carbon source is 5.0-20% of the weight of the precursor powder; the organic water-soluble carbon source is one or more selected from citric acid, glucose, sucrose, polyvinyl alcohol, polyethylene glycol and polyacrylic acid. By selecting a specific carbon source, the precursor powder is spherical compact particles, and the crystallinity is high; meanwhile, when the addition amount of the carbon source is small, the content of carbon formed after pyrolysis is low, and the reduction of oxidation state transition metal elements in the spherical particles is insufficient; while too high a carbon content reduces the capacity of the material in grams.
Further, in the step S3, the addition amount of the alcohol organic solvent is 0.1-20% of the water mass; the alcohol organic solvent is selected from one or more of ethanol, ethylene glycol, methanol, 2-methyl-2-propanol, 2-methyl-3-butene-2-ol, 2-dimethyl-1-propanol, 1-pentene-3-ol, 2-methoxyethanol, 2-trifluoroethanol, 2-ethoxyethanol, 1-pentanol, 2-methyl-1-pentanol, 2-dimethyl-1.1-pentanol, 1-octanol, 1-undecanol and 1, 4-butanediol. The polarity of the alcohol organic solvent is less than that of water, the affinity with a solid interface is strong, the infiltration of the solution on the surface of the precursor powder is facilitated, the infiltration of the solution into pores on the surface layer of the powder is facilitated, and therefore, the uniform and compact coating of the dissolved organic carbon source on the surface of the powder is realized, and a uniform conductive network is formed after sintering; when the addition amount of the alcohol organic solvent is too large, the solution viscosity is increased due to the influence of hydrogen bonds among ions, which is unfavorable for dispersion of the powder.
Further, in step S3, the slurry has a solid content of 40 to 70%. The change of the solid content directly affects the processability of the material, when the solid content is too low, the slurry is easy to layer after standing, and the permeation efficiency of the water-soluble carbon-containing organic matters on a powder interface is reduced; when the solid content is too high, the powder is agglomerated, which is unfavorable for uniform dispersion between solid-liquid interfaces.
Further, in the step S4, the drying temperature is more than or equal to 100 ℃, and the moisture content of the powder is less than or equal to 2%, so that the compactness of the coating layer is prevented from being reduced due to the fact that part of coated carbon is consumed in the sintering process due to the high moisture content; the protective atmosphere is one or more than two of hydrogen, carbon monoxide, nitrogen, argon, nitrogen hydrogen or argon hydrogen; the high-temperature calcination conditions are as follows: the sintering temperature is 450-800 ℃, the heat preservation time is 3-30H, and the surface carbon layer is ensured to completely reduce the oxidation state transition metal in the particle and ensure the sufficient crystal growth of the material.
Another aspect of the invention is to protect a high-compaction polyanionic sodium ion battery positive electrode material prepared by the above preparation method.
The invention relates to a preparation method of a high-compaction polyanion type positive electrode material. The method is characterized in that an alkali metal source, a transition metal source and an anion source which are easy to dissolve in water are uniformly dispersed in water, water and easily-decomposed components in raw materials are removed through high-temperature cracking, and finally, only alkali metal ions, transition metal ions and anions are reserved in precursor powder and form a bonded crystalline state mutually. Then, the precursor powder, water, alcohol substances and water-soluble carbon sources are mixed and stirred, and the mixture is dried and sintered to obtain the high-compaction polyanion type material. .
The high-compaction polyanionic sodium ion battery anode material and the preparation method thereof have the following beneficial effects:
the first and compaction density is high, the invention adopts a water-soluble alkali metal source, a transition metal source and an anion source, the elements are uniformly mixed through water dissolution, and the high-temperature cracking equipment is utilized to realize the rapid separation of solid, liquid and gaseous components, thereby reducing the porosity among particles while realizing the bonding crystallization of alkali metal, transition metal and anion groups, and preparing the high-compaction precursor powder.
Secondly, the specific surface area is small, the ions in the precursor powder are in a highly uniform mixing state, no diffusion process exists among the ions in the subsequent sintering process, the epitaxial growth of the crystal can be realized in a short time, the dependence on the sintering temperature and time is reduced, and the energy consumption cost caused by sintering is effectively saved; the precursor powder after high-temperature pyrolysis has low porosity, small surface area, reduced carbon consumption of the subsequent carbon cladding, high crystallinity, high phase purity, excellent electrochemical performance and high controllability of the batch preparation process of the material formed after sintering. .
Thirdly, the electrochemical performance is excellent, water and an organic carbon source are dissolved and mixed, the polarity of the water-carbon mixed solution is adjusted by utilizing the weak polarity of an alcohol compound, the carbon-containing solution can be ensured to be uniformly adhered and permeated into the surface and pore structure of precursor powder, and after sintering, a uniform and compact conductive layer is formed on the surface of the material.
Drawings
FIG. 1 is a view of Na of practical example 1 4 Fe 3 (PO 4 ) 2 P 2 O 7 A material TEM;
FIG. 2 is Na of comparative example 1 4 Fe 3 (PO 4 ) 2 P 2 O 7 The material TEM.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following further details of the present invention will be described with reference to examples and drawings.
The invention discloses a preparation method of a high-compaction polyanion sodium ion battery anode material, which comprises the following steps:
s1, preparing an ionic precursor solution: mixing and dissolving a water-soluble alkali metal source, a water-soluble transition metal source and an anion source to form a uniform ionic precursor solution;
s2, preparing precursor powder by calcining: calcining and drying the precursor solution by adopting high-temperature cracking equipment to obtain uniform precursor powder;
s3, preparing precursor slurry: mixing and stirring precursor powder, a carbon source, water and an alcohol organic solvent to form uniform precursor slurry;
s4, sintering at a high temperature: and drying the precursor slurry, and then placing the dried precursor slurry in a protective atmosphere for high-temperature calcination treatment to obtain the polyanionic cathode material.
Further, in step S1, the water-soluble alkali metal source is an acidic sodium/lithium salt, and the acidic sodium/lithium salt is one or more selected from sodium chloride/lithium, sodium sulfate/lithium, sodium nitrate/lithium, sodium formate, sodium acetate/lithium, and sodium citrate.
Further, in step S1, the water-soluble transition metal source is a transition metal-based compound and its derivative, and the transition metal-based compound and its derivative are selected from one or more of iron nitrate/cobalt/nickel/manganese, iron chloride/cobalt/nickel/manganese, iron sulfate/cobalt/nickel/manganese, and iron acetate/cobalt/nickel/manganese.
Further, in step S1, the anion source is a phosphorus-containing compound selected from one or more of phosphoric acid, dihydrogen phosphate, pyrophosphoric acid, and metaphosphoric acid.
Further, in step S2, the pyrolysis temperature is not less than 600 ℃.
Further, in the step S3, the carbon source is an organic water-soluble carbon source, and the addition amount of the carbon source is 5.0-20% of the weight of the precursor powder; the organic water-soluble carbon source is one or more selected from citric acid, glucose, sucrose, polyvinyl alcohol, polyethylene glycol and polyacrylic acid.
Further, in the step S3, the addition amount of the alcohol organic solvent is 0.1-20% of the water mass; the alcohol organic solvent is selected from one or more of ethanol, ethylene glycol, methanol, 2-methyl-2-propanol, 2-methyl-3-butene-2-ol, 2-dimethyl-1-propanol, 1-pentene-3-ol, 2-methoxyethanol, 2-trifluoroethanol, 2-ethoxyethanol, 1-pentanol, 2-methyl-1-pentanol, 2-dimethyl-1.1-pentanol, 1-octanol, 1-undecanol and 1, 4-butanediol.
Further, in step S3, the slurry has a solid content of 40 to 70%.
Further, in the step S4, the drying temperature is more than or equal to 100 ℃, and the powder water content is less than or equal to 2%; the protective atmosphere is one or more than two of hydrogen, carbon monoxide, nitrogen, argon, nitrogen hydrogen or argon hydrogen; the high-temperature calcination conditions are as follows: the sintering temperature is 450-800 ℃, and the heat preservation time is 3-30H.
Another aspect of the invention is to protect a high-compaction polyanionic sodium ion battery positive electrode material prepared by the above preparation method.
Application example 1 high compaction Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Synthesis of/C and electrochemical Properties thereof
S1, preparing an ionic precursor solution: water-soluble ferrous sulfate and sodium dihydrogen phosphate are mixed according to a molar ratio of 3:4, adding water for dissolving to form a uniform light green ionic solution;
s2, preparing precursor powder by calcining: calcining and drying the precursor solution by adopting high-temperature cracking equipment, controlling the temperature to 605 ℃ to ensure that sulfur element is completely volatilized in a form of a sulfur-oxygen gaseous compound, and leaving dry crystalline precursor powder;
s3, preparing precursor slurry: mixing the precursor powder, glucose, water and ethylene glycol, wherein the glucose accounts for 10% of the weight of the precursor powder, the ethylene glycol accounts for 5% of the weight of the water, the solid content is controlled to be 50%, and the mixture is uniformly stirred to form viscous slurry;
s4, sintering at a high temperature: and drying the precursor slurry in a vacuum drying oven at 120 ℃ until the water content of the powder is lower than 2%. Then calcining the dried powder in nitrogen atmosphere at 550 ℃ for 10H, and naturally cooling to obtain high-compaction Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 and/C material.
Na is mixed with 4 Fe 3 (PO 4 ) 2 P 2 O 7 After mixing homogenates in a mass ratio of 8:1:1, black paste was coated on aluminum foil using a 150um four-sided fabricator, and the film was dried in a vacuum oven at 100 ℃ for 2 hours. Punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, and taking metal sodium as a counter electrode, wherein the mol/L NaClO is 1mol/L 4 EC+DEC (1:1vol%) +5% FEC is electrolyte, the diaphragm is a PP/PE/PP three-layer diaphragm, and CR is assembled in a glove box2016 type button cell.
FIG. 1 is a high compaction Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 And (C) SEM (scanning electron microscope) of the material, wherein the particles are compact, the porosity is low, the particles are irregular elliptic spherical particles, and the particle size is about 1-3 um. Table 1 shows that the compacted density of the material is as high as 2.1g/cm 3 Compared with 1.81g/cm in comparative example 1 3 The compaction density of the precursor solution is increased by about 16%, which indicates that the particles formed after the precursor solution is pyrolyzed at high temperature are relatively compact, the elements are uniformly arranged, and after carbon-coated sintering, larger single crystal particles are easy to generate and have larger compaction density.
Table 1 shows that application example 1 was highly compacted with Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The reversible discharge capacity of the/C electrode at a rate of 0.1C (1C=129 mAh/g) was 112mAh/g. Compared with comparative example 1 (99.2 mAh/g), the electrode has higher reversible capacity, which indicates that the crystallinity of the high-compaction material is higher, the ion distribution is more uniform, and in the structure formed after sintering, the ion diffusion channel has high continuity, the sodium ion transition energy barrier is low, and the reversible deintercalation capacity is high. In addition, as shown in table 1, the electrode exhibited excellent cycle stability with a capacity retention of 100% over 1000 weeks of cycle. Compared with comparative example 1 (97.8%), the higher capacity retention of the electrode is that the electrode has compact particles, low porosity, small contact area with electrolyte and low interface side reaction, thereby increasing the structural stability in the long cycle process.
Application example 2 high compaction Na 4 MnV(PO 4 ) 3 Synthesis of/C and electrochemical Properties thereof
S1, preparing an ionic precursor solution: water-soluble manganese sulfate, ammonium metavanadate, sodium dihydrogen phosphate and sodium hydroxide are mixed according to the mole ratio of 1:1:3:1, adding water for dissolving to form a uniform dark red ionic solution;
s2, preparing precursor powder by calcining: calcining and drying the precursor solution by adopting high-temperature cracking equipment, controlling the temperature at 650 ℃, ensuring that elements such as sulfur, ammonia and the like are completely volatilized in the form of sulfur or nitrogen-oxygen gaseous compounds, and leaving dry crystalline precursor powder;
s3, preparing precursor slurry: mixing the precursor powder, citric acid, water and ethanol, wherein the citric acid accounts for 12% of the precursor powder by weight, the ethanol accounts for 7% of the precursor powder by weight, the solid content is controlled to be 55% by weight, and stirring uniformly to form a viscous slurry;
s4, sintering at a high temperature: and drying the precursor slurry in a vacuum drying oven at 150 ℃ until the water content of the powder is lower than 2%. Then calcining the dried powder in argon atmosphere at 700 ℃ for 8H, and naturally cooling to obtain high-compaction Na 4 MnV(PO 4 ) 3 and/C material.
Na is mixed with 4 MnV(PO 4 ) 3 After mixing to homogenize in a mass ratio of 8:1:1, the black paste was coated on aluminum foil using a 150um four-sided fabricator, and the film was dried in a vacuum oven at 100 ℃ for 2 hours. Punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, and taking metal sodium as a counter electrode, wherein the mol/L NaClO is 1mol/L 4 EC+DEC (1:1vol%) +5% FEC was electrolyte, and the separator was a PP/PE/PP three-layer separator, and a CR2016 type coin cell was assembled in a glove box.
Table 1 shows the results of Na of application example 2 4 MnV(PO 4 ) 3 The compacted density of the material/C is 2.25g/cm 3 Compared with comparative example 21, the porosity of the material prepared by the process is about 20.3%, which indicates that the material prepared by the process has low porosity, larger grain size and denser grain size. In addition, the reversible specific capacity of the electrode was 110.5mAh/g at a rate of 0.1C (1C=120 mAh/g), which was higher than that of comparative example 2 (102.8 mAh/g). The capacity retention rate of the electrode after 1000 weeks is 98.5 percent, which is higher than 91.2 percent in comparative example 21, which shows that the high-compaction powder material has low porosity, small contact area with electrolyte, reduced leaching amount of manganese ions on the surface of the material, improved structural stability and greatly improved cycling stability.
Application example 3 high compaction Na 3 MnTi(PO 4 ) 3 Synthesis of/C and electrochemical Properties thereof
S1, preparing an ionic precursor solution: water-soluble manganese sulfate, titanyl sulfate and sodium dihydrogen phosphate are mixed according to the mole ratio of 1:1:3, adding water for dissolving to form uniform brown ionic solution;
s2, preparing precursor powder by calcining: calcining and drying the precursor solution by adopting high-temperature cracking equipment, controlling the temperature at 700 ℃ to ensure that sulfur element is completely volatilized in a form of a sulfur-oxygen gaseous compound, and leaving dry crystalline precursor powder;
s3, preparing precursor slurry: mixing precursor powder, sucrose, water and 2-methyl-2-propanol, wherein the sucrose accounts for 7% of the weight of the precursor powder, the 2-methyl-2-propanol accounts for 3% of the weight of the water, the solid content is controlled to be 60%, and stirring uniformly to form viscous slurry;
s4, sintering at a high temperature: and drying the precursor slurry in a vacuum drying oven at 170 ℃ until the water content of the powder is lower than 2%. Then calcining the dried powder in nitrogen atmosphere at 780 ℃ for 10H, and naturally cooling to obtain high-compaction Na 3 MnTi(PO 4 ) 3 and/C material.
Na is mixed with 3 MnTi(PO 4 ) 3 After mixing to homogenize in a mass ratio of 8:1:1, the black paste was coated on aluminum foil using a 150um four-sided fabricator, and the film was dried in a vacuum oven at 100 ℃ for 2 hours. Punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, and taking metal sodium as a counter electrode, wherein the mol/L NaClO is 1mol/L 4 EC+DEC (1:1vol%) +5% FEC was electrolyte, and the separator was a PP/PE/PP three-layer separator, and a CR2016 type coin cell was assembled in a glove box.
The results in Table 1 show that Na of application example 3 3 MnTi(PO 4 ) 3 The compacted density of the material/C is 2.13g/cm 3 About 22.4% higher than comparative example 3. In addition, the reversible specific capacity of the electrode is 165.2mAh/g at the rate of 0.1C (1 C=170 mAh/g), the capacity retention rate of the electrode is 93.3% after 1000 weeks of circulation, and the electrode shows excellent electrochemical performance, which is related to high compaction density, high crystallization integrity, low porosity and few interfacial side reactions of the material synthesized by the process.
Comparative example 1Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Synthesis of/C and electrochemical Properties thereof
Step 1: adding water into water-soluble ferrous sulfate, sodium dihydrogen phosphate, glucose and ethylene glycol according to the proportion in application example 1 to dissolve to form a uniform light green ionic precursor solution;
step 2: the precursor solution was baked in a 120 ℃ vacuum oven to a powder water content of less than 2%. Then calcining the dried powder in nitrogen atmosphere at 550 ℃ for 10H, and naturally cooling to obtain Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 and/C material.
Na is mixed with 4 Fe 3 (PO 4 ) 2 P 2 O 7 After mixing homogenates in a mass ratio of 8:1:1, black paste was coated on aluminum foil using a 150um four-sided fabricator, and the film was dried in a vacuum oven at 100 ℃ for 2 hours. Punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, and taking metal sodium as a counter electrode, wherein the mol/L NaClO is 1mol/L 4 EC+DEC (1:1vol%) +5% FEC was electrolyte, and the separator was a PP/PE/PP three-layer separator, and a CR2016 type coin cell was assembled in a glove box.
FIG. 2 is Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 And (C) SEM (scanning electron microscope) pictures of materials, wherein the particles are loose, the porosity is higher, the particles are irregular secondary particle aggregates, and primary particles are about 100-200 nm. Table 1 shows that the compacted density of the material is only 1.81g/cm 3 The main reason for this is that the carbon source such as glucose is added at the initial stage and can be uniformly dispersed among the whole elements, and carbonization during sintering of the material can hinder the growth of the material particles, resulting in the formation of a large number of fine single crystal particles, and larger pores remain among the particles, resulting in a decrease in the compacted density.
Shown in Table 1, na of comparative example 1 4 Fe 3 (PO 4 ) 2 P 2 O 7 The reversible discharge capacity of the/C electrode at a rate of 0.1C (1c=129 mAh/g) was 99.2mAh/g. The electrode capacity exerted was lower than that of application example 1 (112 mAh/g), mainly because of the impeding effect of the pyrolytic carbon layer on grain growth, resulting in a large amount of particles existing in an amorphous or disordered state,partial site ion diffusion channels disappear, sodium ion deintercalation is blocked, the material is deactivated, and the capacity is reduced. In addition, table 1 shows that the electrode has a capacity retention rate of 97.8% after 1000 weeks of circulation, and the circulation stability is lower than that of comparative example 1 of application example 1, which indicates that the material has more pores, the contact area with the electrolyte is too large due to loose particles, the side reaction is increased, the structure is easily cracked during the circulation, and the circulation stability is reduced.
Comparative example 2Na 4 MnV(PO 4 ) 3 Synthesis of/C and electrochemical Properties thereof
Step 1: dissolving water-soluble manganese sulfate, ammonium metavanadate, sodium dihydrogen phosphate, sodium hydroxide, citric acid and ethanol in water according to the proportion in application example 2 to form a uniform deep red ionic precursor solution;
step 2: the precursor solution was baked in a vacuum oven at 150 ℃ until the powder water content was below 2%. Then calcining the dried powder in argon atmosphere at 700 ℃ for 8H, and naturally cooling to obtain Na 4 MnV(PO 4 ) 3 and/C material.
Na is mixed with 4 MnV(PO 4 ) 3 After mixing to homogenize in a mass ratio of 8:1:1, the black paste was coated on aluminum foil using a 150um four-sided fabricator, and the film was dried in a vacuum oven at 100 ℃ for 2 hours. Punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, and taking metal sodium as a counter electrode, wherein the mol/L NaClO is 1mol/L 4 EC+DEC (1:1vol%) +5% FEC was electrolyte, and the separator was a PP/PE/PP three-layer separator, and a CR2016 type coin cell was assembled in a glove box.
The results in Table 1 show that Na of comparative example 2 4 MnV(PO 4 ) 3 The compacted density of the material/C is only 1.87g/cm 3 Lower than application example 2, indicates that the initial carbon source incorporation causes excessive material gap after sintering, reduced grain size, reduced crystallinity, and reduced compaction density. In addition, at a rate of 0.1C (1c=120 mAh/g), the reversible specific capacity of the electrode was only 102.8mAh/g, and the capacity retention of the electrode was only 91.2% over 1000 cycles, indicating more gaps and low compacted density materials, andthe contact area of the electrolyte can be increased, so that interface manganese ions are dissolved into the electrolyte under the influence of the Taylor effect in the sodium intercalation process, and the cycling stability of the material is greatly reduced.
Comparative example 3 Na 3 MnTi(PO 4 ) 3 Synthesis of/C and electrochemical Properties thereof
Step 1: dissolving water-soluble manganese sulfate, titanyl sulfate, sodium dihydrogen phosphate, sucrose and 2-methyl-2-propanol in water according to the proportion in application example 3 to form a uniform brown ionic solution;
step 2: and drying the precursor slurry in a vacuum drying oven at 170 ℃ until the water content of the powder is lower than 2%. Then calcining the dried powder in nitrogen atmosphere at 780 ℃ for 10H, and naturally cooling to obtain Na 3 MnTi(PO 4 ) 3 and/C material.
Na is mixed with 3 MnTi(PO 4 ) 3 After mixing to homogenize in a mass ratio of 8:1:1, the black paste was coated on aluminum foil using a 150um four-sided fabricator, and the film was dried in a vacuum oven at 100 ℃ for 2 hours. Punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, and taking metal sodium as a counter electrode, wherein the mol/L NaClO is 1mol/L 4 EC+DEC (1:1vol%) +5% FEC was electrolyte, and the separator was a PP/PE/PP three-layer separator, and a CR2016 type coin cell was assembled in a glove box.
The results in Table 1 show that Na of comparative example 3 3 MnTi(PO 4 ) 3 The compacted density of the material/C is only 1.74g/cm 3 Lower than application example 1. In addition, the reversible specific capacity of the electrode is 146.1mAh/g at the rate of 0.1C (1 C=170 mAh/g), and the capacity retention rate of the electrode is only 75.7% after 1000 weeks of circulation, so that the electrochemical performance is poor, and the electrode is related to high porosity, low crystallinity and high side reaction degree of an interface and electrolyte in the sodium removing process of the material synthesized by the process.
TABLE 1 Performance test results
The foregoing examples are merely exemplary embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.
Claims (10)
1. The preparation method of the high-compaction polyanionic sodium ion battery anode material is characterized by comprising the following steps:
s1, preparing an ionic precursor solution: mixing and dissolving a water-soluble alkali metal source, a water-soluble transition metal source and an anion source to form a uniform ionic precursor solution;
s2, preparing precursor powder by calcining: calcining and drying the precursor solution by adopting high-temperature cracking equipment to obtain uniform precursor powder;
s3, preparing precursor slurry: mixing and stirring precursor powder, a carbon source, water and an alcohol organic solvent to form uniform precursor slurry;
s4, sintering at a high temperature: and drying the precursor slurry, and then placing the dried precursor slurry in a protective atmosphere for high-temperature calcination treatment to obtain the polyanionic cathode material.
2. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in step S1, the water-soluble alkali metal source is an acidic sodium/lithium salt, and the acidic sodium/lithium salt is one or more selected from sodium chloride/lithium, sodium sulfate/lithium, sodium nitrate/lithium, sodium formate, sodium acetate/lithium, and sodium citrate.
3. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in step S1, the water-soluble transition metal source is a transition metal-based compound and its derivative, and the transition metal-based compound and its derivative are one or more selected from iron nitrate/cobalt/nickel/manganese, iron chloride/cobalt/nickel/manganese, iron sulfate/cobalt/nickel/manganese, and iron acetate/cobalt/nickel/manganese.
4. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in step S1, the anion source is a phosphorus-containing compound selected from one or more of phosphoric acid, dihydrogen phosphate, pyrophosphoric acid, and metaphosphoric acid.
5. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in the step S2, the pyrolysis temperature is more than or equal to 600 degrees.
6. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in the step S3, the carbon source is an organic water-soluble carbon source, and the addition amount of the carbon source is 5.0-20% of the weight of the precursor powder; the organic water-soluble carbon source is one or more selected from citric acid, glucose, sucrose, polyvinyl alcohol, polyethylene glycol and polyacrylic acid.
7. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in the step S3, the addition amount of the alcohol organic solvent is 0.1-20% of the water mass; the alcohol organic solvent is selected from one or more than two of ethanol, ethylene glycol, methanol, 2-methyl-2-propanol, 2-methyl-3-butene-2-alcohol, 2-dimethyl-1-propanol, 1-pentene-3 alcohol, 2-methoxyethanol, 2-trifluoroethanol, 2-ethoxyethanol, 1-amyl alcohol, 2-methyl-1-amyl alcohol, 2-dimethyl-1.1-amyl alcohol, 1-octanol, 1-undecanol and 1, 4-butanediol.
8. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in the step S3, the solid content of the slurry is 40-70%.
9. The method for preparing the high-compaction polyanionic sodium ion battery positive electrode material according to claim 1, wherein the method comprises the following steps: in the step S4, the drying temperature is more than or equal to 100 ℃, and the powder water content is less than or equal to 2%; the protective atmosphere is one or more than two of hydrogen, carbon monoxide, nitrogen, argon, nitrogen hydrogen or argon hydrogen; the high-temperature calcination conditions are as follows: the sintering temperature is 450-800 ℃, and the heat preservation time is 3-30H.
10. A high-compaction polyanionic sodium ion battery cathode material, characterized in that it is prepared by the preparation method according to any one of claims 1 to 9.
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