CN117080379A - 钠离子电池正极材料、其制备方法、钠离子电池正极及钠离子电池 - Google Patents
钠离子电池正极材料、其制备方法、钠离子电池正极及钠离子电池 Download PDFInfo
- Publication number
- CN117080379A CN117080379A CN202310890588.1A CN202310890588A CN117080379A CN 117080379 A CN117080379 A CN 117080379A CN 202310890588 A CN202310890588 A CN 202310890588A CN 117080379 A CN117080379 A CN 117080379A
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- China
- Prior art keywords
- positive electrode
- ion battery
- sodium ion
- electrode material
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 71
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 62
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000011247 coating layer Substances 0.000 claims abstract description 51
- 239000011734 sodium Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 39
- 239000002243 precursor Substances 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000002270 dispersing agent Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000003746 solid phase reaction Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract 4
- 239000010405 anode material Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000003570 air Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229960002413 ferric citrate Drugs 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- HUTBITLDXCEAPZ-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;iron Chemical compound [Fe].OC(=O)CC(O)(C(O)=O)CC(O)=O HUTBITLDXCEAPZ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 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 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 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 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 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 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011640 ferrous citrate Substances 0.000 description 1
- 235000019850 ferrous citrate Nutrition 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 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 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WRMXOVHLRUVREB-UHFFFAOYSA-N phosphono phosphate;tributylazanium Chemical compound OP(O)(=O)OP([O-])([O-])=O.CCCC[NH+](CCCC)CCCC.CCCC[NH+](CCCC)CCCC WRMXOVHLRUVREB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 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 description 1
- 235000011083 sodium citrates Nutrition 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- YNIRKEZIDLCCMC-UHFFFAOYSA-K trisodium;phosphate;hydrate Chemical compound [OH-].[Na+].[Na+].[Na+].OP([O-])([O-])=O YNIRKEZIDLCCMC-UHFFFAOYSA-K 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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Abstract
本申请公开了一种钠离子电池正极材料、其制备方法、钠离子电池正极及钠离子电池,正极材料包括内核及包覆内核的包覆层,内核包括层状氧化物,包覆层的通式为Na4Fe3‑xMx(PO4)2‑ yP2O7Fy,0≤x≤3,0≤y≤1,x、y的取值满足化学式的电荷平衡,M为选自Ni、Mn、Co、Cu、Zn、Mg、Al、Ca、Sr、Ce、Ti、Zr、Sn、V、Nb、Sb中的一种或多种。上述正极材料降低了正极材料的碱性,并减少了其与电解液之间的副反应,解决了电芯产气的问题,提高了正极材料的循环稳定性;另外,包覆层能够提供可逆容量,使正极材料的整体能量密度降低控制在5%以内。
Description
技术领域
本申请涉及钠离子电池技术领域,特别是涉及一种钠离子电池正极材料、其制备方法、钠离子电池正极及钠离子电池。
背景技术
钠离子电池因钠资源丰富、成本低、安全性能好等优势在储能领域有着广泛的应用前景,其工作原理与锂离子电池相似,利用钠离子在正负极之间的嵌入脱出来实现能量的存储与释放。
目前由于层状氧化物克容量高,能够与现有制造工艺匹配,广泛用于钠离子电池的正极材料。但层状氧化物的碱性较强,在电池中成膜不稳定,容易造成浆料凝胶、电芯产气、循环衰减等问题。
发明内容
本发明提供了一种钠离子电池正极材料、其制备方法、钠离子电池正极及钠离子电池,以解决现有技术中钠离子电池正极材料碱性强而导致的浆料凝胶、电芯产气、循环衰减的技术问题。
为达到上述目的,本发明提供的技术方案如下:
本发明的第一方面,提供了一种钠离子电池正极材料,包括内核及包覆所述内核的包覆层,所述内核包括层状氧化物,所述包覆层的通式为Na4Fe3-xMx(PO4)2-yP2O7Fy,其中0≤x≤3,0≤y≤1,x、y的取值满足化学式的电荷平衡,M为选自Ni、Mn、Co、Cu、Zn、Mg、Al、Ca、Sr、Ce、Ti、Zr、Sn、V、Nb、Sb中的一种或多种。
进一步地,所述包覆层的厚度为1nm~500nm。
进一步地,所述包覆层与所述层状氧化物的质量比为1∶4~100。
进一步地,所述层状氧化物的通式为NazRO2,其中0.5≤z≤1.5,R为选自Fe、Ni、Mn、Cu、Co、Ru、Ir、Sn、Cr、Nb、Mo中的一种或多种。
进一步地,所述层状氧化物的平均粒径为1μm~50μm。
进一步地,所述正极材料的pH值为7~11.5。
本发明的第二方面,提供了上述钠离子电池正极材料的制备方法,包括以下步骤:S1、将钠源、铁源、M源、磷源、氟源、碳源混合反应制备得到前驱体;S2、将包括所述层状氧化物的所述内核与所述步骤S1制得的所述前驱体混合并加入分散剂预分散,在保护气中350℃~600℃温度下保温,在所述层状氧化物上形成所述包覆层,所述包覆层为Na4Fe3-xMx(PO4)2-yP2O7Fy,即得到所述正极材料。
进一步地,所述步骤S1中,利用钠源、铁源、M源、磷源、氟源、碳源制备所述前驱体的方法选自固相反应法、溶胶凝胶法、喷雾干燥法、共沉淀法中的一种。
进一步地,所述步骤S2中,所述层状氧化物、所述前驱体、所述分散剂的质量比为47~89∶1~3∶10~50。
进一步地,所述分散剂包括乙二醇。
进一步地,所述分散剂还包括选自乙醇、丁醇、丁二醇、戊醇、丙酮、甲乙酮、甲基异丁酮、环己酮、异佛尔酮、乙醚、四氢呋喃、1,4-二氧六环、戊烷、己烷、戊烯、己烯中一种或多种溶剂。
本发明的第三方面,提供了一种钠离子电池正极,包括集流体、导电剂、粘结剂及上述的正极材料,所述集流体的至少一个表面上包含所述导电剂、所述粘结剂及所述正极材料。
本发明的第四方面,提供了一种钠离子电池,包括上述的钠离子电池正极。
本发明提供的钠离子电池正极材料,包覆层对层状氧化物包覆均匀,其对层状氧化物提供保护,降低了正极材料的碱性,并减少了其与电解液之间的副反应,减少了有害副产物在正极表面的堆积,解决了电芯产气的问题,提高了正极材料的循环稳定性;另外,包覆层能够提供可逆容量,使正极材料的整体能量密度降低控制在5%以内。本发明提供的钠离子电池正极材料的制备方法,制备前驱体可用多种方法,降低了制备难度,工艺过程简单,易广泛应用。
附图说明
为了更清楚地说明本申请实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请中记载的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明实施例1中包覆前层状氧化物的SEM图;
图2为本发明实施例1中包覆后正极材料的SEM图;
图3为本发明实施例1中Na4Fe3(PO4)2P2O7包覆的正极材料XRD图;
图4为本发明实施例1中Na4Fe3(PO4)2P2O7包覆的正极材料扣电测试结果图。
具体实施方式
为了使本领域的技术人员更好地理解本申请中的技术方案,下面将对本申请实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本申请的一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
须知,本说明书附图所绘示的结构、比例、大小等,均仅用以配合说明书所揭示的内容,以供熟悉此技术的人士了解与阅读,并非用以限定本申请可实施的限定条件,故不具技术上的实质意义,任何结构的修饰、比例关系的改变或大小的调整,在不影响本申请所能产生的功效及所能达成的目的下,均应仍落在本申请所揭示的技术内容所能涵盖的范围内。
本申请实施例的第一方面,提供一种钠离子电池正极材料,包括内核及包覆内核的包覆层,内核包括层状氧化物,包覆层的通式为Na4Fe3-xMx(PO4)2-yP2O7Fy,其中0≤x≤3,0≤y≤1,x、y的取值满足化学式的电荷平衡,M为选自Ni、Mn、Co、Cu、Zn、Mg、Al、Ca、Sr、Ce、Ti、Zr、Sn、V、Nb、Sb中的一种或多种。
为了解决钠离子电池的正极材料碱性较强的问题,一般会采用两种或两种以上材料通过球磨方法混合作为正极材料的方案,即将两种或两种以上的材料物理混合,但上述方案中正极材料仍然会与电解液之间发生副反应,不能完全解决其碱性强的技术问题。
本申请实施例采用包覆层包覆的层状氧化物作为正极材料,将层状氧化物包覆在内部避免了其与电解液的接触从而避免副反应的发生,减少了有害副产物在正极表面的堆积,解决了电芯产气的问题,提高了正极材料的循环稳定性;另外,包覆层能够提供可逆容量,使正极材料的整体能量密度降低控制在5%以内。本申请实施例的包覆型正极材料应用于非水系钠离子电池中。
具体地,包覆层的厚度为1nm~500nm。可以理解地,包覆层位于层状氧化物的外部,用于避免层状氧化物的碱性问题,且避免层状氧化物与电解液直接接触,包覆层需要均匀地分布,且最小厚度满足将层状氧化物与电解液隔开的目的;但厚度不能太大,即包覆层与层状氧化物的质量比不能太大,避免影响正极材料的整体能量密度。具体地,包覆层与层状氧化物的质量比为1∶4~100。
一些实施例中,层状氧化物的通式为NazRO2,其中0.5≤z≤1.5,R为选自Fe、Ni、Mn、Cu、Co、Ru、Ir、Sn、Cr、Nb、Mo中的一种或多种。上述层状氧化物都能够采用本申请实施例的包覆方法制得正极材料。具体地,层状氧化物的平均粒径为1μm~50μm。
进一步地,正极材料的pH值为7~11.5。一般情况下,层状氧化物作为正极材料时其pH值大于等于12,而本申请实施例采用包覆层包覆内核的结构作为正极材料,能够将正极材料的pH值降低至7~11.5,避免层状氧化物的碱性问题。
本申请实施例的第二方面,提供一种上述钠离子电池正极材料的制备方法,包括以下步骤:
S1、将钠源、铁源、M源、磷源、氟源、碳源混合反应制备得到前驱体;
S2、将包括层状氧化物的内核与步骤S1制得的前驱体混合并加入分散剂预分散,在保护气中350℃~600℃温度下保温,在层状氧化物上形成包覆层,包覆层为Na4Fe3-xMx(PO4)2-yP2O7Fy,即得到正极材料。
本申请实施例中,层状氧化物与前驱体在保护气环境下,保温后能够得到层状氧化物完全被包裹的正极材料,包覆层能够隔绝层状氧化物与外界空气、水及电解液的直接接触。现有技术中的物理混合使用球磨法,最终为颗粒与颗粒之间的混合,无法实现上述的完全包覆。
其中,钠源、铁源、M源、磷源、氟源、碳源的一种或多种可以包含在同一原料中,也可以包含在多种不同的原料中,此处不作限定。根据所选原料的不同,可以使用不同的制备方法得到上述前驱体。
具体地,钠源包含但不限于磷酸二氢钠、磷酸钠、碳酸钠、硝酸钠、草酸钠、醋酸钠、硫酸钠、氢氧化钠、甲酸钠、柠檬酸钠、焦磷酸钠、焦磷酸二氢钠中的一种或多种。铁源包含但不限于铁粉、柠檬酸铁、柠檬酸亚铁、硝酸铁、硝酸亚铁、硫酸铁、硫酸亚铁、氯化铁、氯化亚铁、四氧化三铁、三氧化二铁、氧化亚铁、草酸铁、草酸亚铁、乙酸铁、磷酸铁、焦磷酸铁、硫酸亚铁铵中的一种或多种。M源包含但不限于M的氧化物、碳酸盐、氢氧化物、氟化物、硝酸盐、硝酸盐的水合化合物、乙酸盐、乙酸盐的水合物中的一种或多种。磷源包含但不限于焦磷酸钠、焦磷酸二氢钠、磷酸二氢钠、磷酸钠、磷酸钠的水合物中的一种或多种。氟源包含但不限于氟化锂、氟化钠、氟化M中的一种或多种。碳源包含但不限于草酸、抗坏血酸、甲醛、乙醛、正丁醛、乳酸、柠檬酸、苹果酸、乙二酸、己二酸、柠檬酸、可溶性淀粉、抗坏血酸、蔗糖、葡萄糖中的一种或多种。
一些实施例中,步骤S1中,利用钠源、铁源、M源、磷源、氟源、碳源制备前驱体的方法选自固相反应法、溶胶凝胶法、喷雾干燥法、共沉淀法中的一种。根据所选原料的不同,可以使用不同的制备方法得到上述前驱体,原料与制备方法的对应参见表1。
表1原料与制备方法的对应表
一些实施例中,分散剂包括乙二醇。进一步地,分散剂还包括水、醇类、酮类、烷烃类、烯烃类中的一种或多种。具体地,醇类选自乙二醇、乙醇、丁醇、丁二醇、戊醇中的一种或多种。酮类选自丙酮、甲乙酮、甲基异丁酮、环己酮、异佛尔酮中的一种或多种。醚类选自乙醚、四氢呋喃、1,4-二氧六环中的一种或多种。烷烃类选自戊烷或己烷。烯烃类选自戊烯或己烯。
一些实施例中,步骤S2中,层状氧化物、混合液、分散剂的质量比为47~89∶1~3∶10~50。本申请实施例中,在还原气体的环境中,350℃~600℃温度下保温,使混合液包覆于层状氧化物的表面形成包覆层,分散剂则会挥发出去,即可得到正极材料。
本申请实施例的第三方面,还提供了一种钠离子电池正极,包括集流体、导电剂、粘结剂及上述的正极材料,集流体的至少一个表面上包含导电剂、粘结剂、正极材料形成的混合物。
本申请实施例的第四方面,还提供了一种钠离子电池,包括上述钠离子电池正极。
以下实施例中各试剂均为市售。
实施例1
一种钠离子电池正极材料,包括内核及包覆内核的包覆层,内核包括层状氧化物NaNi0.3Fe0.5Mn0.2O2;包覆层为Na4Fe3(PO4)2P2O7;包覆层的厚度为20nm,包覆层与层状氧化物的质量比为1∶10,层状氧化物的平均粒径为20μm。该正极材料的pH值为9.7。
上述钠离子电池正极材料的制备方法,包括以下步骤:
1、按Na4Fe3(PO4)2P2O7的化学计量比,使用溶胶-凝胶法制备前驱体。
将7.3kg柠檬酸铁和5.6kg NaH2PO4·2H2O混合于去离子水中,搅拌溶解,并在60℃下经充分搅拌后得到凝胶,然后将凝胶置于马弗炉中,在空气氛中120℃下焙烧12小时后得到前驱体。
2、将5kg层状氧化物NaNi0.3Fe0.5Mn0.2O2、0.5kg制得的前驱体混合并加入20kg分散剂乙二醇预分散,在氢气氛围中升温至500℃下保温10h,即得到上述正极材料。
分别采用扫描电子显微镜测试上述包覆前层状氧化物及包覆后的正极材料,测试结果参照图1和图2,从图中可以看出Na4Fe3(PO4)2P2O7均匀地包覆于层状氧化物的表面。图3为Na4Fe3(PO4)2P2O7包覆的正极材料XRD图,也可以看出层状氧化物与前驱体形成包覆。
实施例2
一种钠离子电池正极材料,包括内核及包覆内核的包覆层,内核包括层状氧化物NaCr0.25Ni0.25Fe0.25Ti0.25O2;包覆层为Na4Fe2.9Mn0.1(PO4)1.8P2O7F0.2;包覆层的厚度为23nm,包覆层与层状氧化物的质量比为1∶30,层状氧化物的平均粒径为20μm。该正极材料的pH值为9.4。
上述钠离子电池正极材料的制备方法,包括以下步骤:
1、按Na4Fe2.9Mn0.1(PO4)1.8P2O7F0.2的化学计量比,使用共沉淀法制备前驱体。
按化学计量比,将5.2kg Fe(NO3)2、5.6kg NaH2PO4·2H2O、0.18kg Mn(NO3)2、0.18kg NaF置于去离子水中混合均匀,得到总浓度为1mol/L的盐溶液。配置0.5mol/L的氨水溶液和2mol/L的NaOH溶液,分别作为络合剂和沉淀剂,然后将11L盐溶液、15L络合剂和1.4L沉淀剂同时注入反应容器中,进行共沉淀反应,共沉淀反应温度为50℃。通过调节NaOH溶液流速将pH值控制在11.0。将所得沉淀经离心分离、干燥后得后得前驱体。
2、将5kg层状氧化物NaCr0.25Ni0.25Fe0.25Ti0.25O2、0.5kg制得前驱体混合并加入20kg分散剂预分散,其中分散剂为乙二醇和环己烯体积比10∶0.5的混合液,在氢气氛围中升温至500℃下保温10h,即得到上述正极材料。
实施例3
一种钠离子电池正极材料,包括内核及包覆内核的包覆层,内核包括层状氧化物NaNi0.32Fe0.13Co0.15Mn0.4O2;包覆层为Na4Fe2.9Ni0.1(PO4)1.8P2O7F0.2;包覆层的厚度为18nm,包覆层与层状氧化物的质量比为1∶10,层状氧化物的平均粒径为30μm。该正极材料的pH值为10.0。
上述钠离子电池正极材料的制备方法,包括以下步骤:
1、按Na4Fe2.9Ni0.1(PO4)1.8P2O7F0.2化学计量比,使用直接固相反应法制备前驱体。
按化学计量比,将2.1kg氧化亚铁、5.6kg NaH2PO4·2H2O和0.097kg NiF2混合均匀,进行球磨,其中球磨时间为10小时,转速为400rpm,再将球磨后的混合物置于马弗炉中,在空气氛中300℃下焙烧15小时后得前驱体。
2、将5kg层状氧化物NaNi0.32Fe0.13Co0.15Mn0.4O2、0.5kg制得的前驱体混合并加入20kg分散剂乙二醇预分散,在氢气氛围中升温至500℃下保温10h,即得到上述正极材料。
实施例4
一种钠离子电池正极材料,包括内核及包覆内核的包覆层,内核包括层状氧化物NaNi0.48Mn0.3Ti0.2Zr0.02O2;包覆层为Na4Fe2.7Cu0.1Zn0.1(PO4)1.8P2O7F0.2;包覆层的厚度为30nm,包覆层与层状氧化物的质量比为1∶12,层状氧化物的平均粒径为18μm。该正极材料的pH值为10.6。
上述钠离子电池正极材料的制备方法,包括以下步骤:
1、按Na4Fe2.7Cu0.1Zn0.1(PO4)1.8P2O7F0.2化学计量比,使用喷雾干燥法制得前驱体。
按化学计量比,将6.9kg柠檬酸铁、5.6kg NaH2PO4·2H2O、0.19kg Cu(NO3)2、0.14kgZnCl2和0.084kg NaF混合于去离子水中,经充分搅拌后得到混合溶液,对混合溶液进行喷雾干燥,其中喷雾干燥仪的进口温度180℃,出口温度110℃,干燥后置于马弗炉中,在空气氛中120℃下焙烧12小时后得到前驱体。
2、将6kg层状氧化物NaNi0.48Mn0.3Ti0.2Zr0.02O2、0.5kg制得的前驱体混合并加入20kg分散剂乙二醇预分散,在氢气氛围中升温至500℃下保温10h,即得到上述正极材料。
实施例5
一种钠离子电池正极材料,包括内核及包覆内核的包覆层,内核包括层状氧化物NaNi0.6Fe0.3Mn0.1O2;包覆层为Na4Fe3(PO4)2P2O7;包覆层的厚度为22nm,包覆层与层状氧化物的质量比为1∶15,层状氧化物的平均粒径为16μm。该正极材料的pH值为9.5。
上述钠离子电池正极材料的制备方法,包括以下步骤:
1、按Na4Fe3(PO4)2P2O7的化学计量比,使用溶胶-凝胶法制备前驱体。
将7.3kg柠檬酸铁和5.6kg NaH2PO4·2H2O混合于去离子水中,搅拌溶解,并在60℃下经充分搅拌后得到凝胶,然后将凝胶置于马弗炉中,在空气氛中120℃下焙烧12小时后得到前驱体。
2、将7.5kg层状氧化物NaNi0.6Fe0.3Mn0.1O2、0.5kg制得的前驱体混合并加入20kg分散剂预分散,其中分散剂为乙二醇和丙酮体积比10∶1的混合液,在氢气氛围中升温至500℃下保温10h,即得到上述正极材料。
将实施例1至5的正极材料制备得到扣式电池。对实施例1至5制作的扣式电池及普通球磨法制备正极材料的钠离子电池进行扣电循环测试,测试结果参见表2,实施例1与普通球磨法制备正极材料的钠离子电池测试结果对照图4。由图4可以看出,在循环10次后,采用上述实施例的钠离子电池的容量仍基本保持不变,而未经包覆的钠离子电池的容量则明显能够看出有了明显的降低,其容量保持率均位于90%以下。
表2实施例1至5的扣式电池与普通球磨法制备正极材料的钠离子电池循环10次后的测试结果
项目 | 容量保持率(%) | 项目 | 容量保持率(%) |
实施例1 | 100% | 实施例4 | 98% |
实施例2 | 98% | 实施例5 | 94% |
实施例3 | 95% | 对比例 | 88% |
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (13)
1.一种钠离子电池正极材料,其特征在于:包括内核及包覆所述内核的包覆层,所述内核包括层状氧化物,所述包覆层的通式为Na4Fe3-xMx(PO4)2-yP2O7Fy,其中0≤x≤3,0≤y≤1,x、y的取值满足化学式的电荷平衡,M为选自Ni、Mn、Co、Cu、Zn、Mg、Al、Ca、Sr、Ce、Ti、Zr、Sn、V、Nb、Sb中的一种或多种。
2.根据权利要求1所述的钠离子电池正极材料,其特征在于,所述包覆层的厚度为1nm~500nm。
3.根据权利要求1所述的钠离子电池正极材料,其特征在于,所述包覆层与所述层状氧化物的质量比为1∶4~100。
4.根据权利要求1所述的钠离子电池正极材料,其特征在于,所述层状氧化物的通式为NazRO2,其中0.5≤z≤1.5,R为选自Fe、Ni、Mn、Cu、Co、Ru、Ir、Sn、Cr、Nb、Mo中的一种或多种。
5.根据权利要求4所述的钠离子电池正极材料,其特征在于,所述层状氧化物的平均粒径为1μm~50μm。
6.根据权利要求1至5任意一项所述的钠离子电池正极材料,其特征在于,所述正极材料的pH值为7~11.5。
7.权利要求1至6任意一项所述的钠离子电池正极材料的制备方法,其特征在于,包括以下步骤:
S1、将钠源、铁源、M源、磷源、氟源、碳源混合反应制备得到前驱体;
S2、将包括所述层状氧化物的所述内核与所述步骤S1制得的所述前驱体混合并加入分散剂预分散,在保护气中350℃~600℃温度下保温,在所述层状氧化物上形成所述包覆层,所述包覆层为Na4Fe3-xMx(PO4)2-yP2O7Fy,即得到所述正极材料。
8.根据权利要求7所述的钠离子电池正极材料的制备方法,其特征在于,所述步骤S1中,利用钠源、铁源、M源、磷源、氟源、碳源制备所述前驱体的方法选自固相反应法、溶胶凝胶法、喷雾干燥法、共沉淀法中的一种。
9.根据权利要求7所述的钠离子电池正极材料的制备方法,其特征在于,所述步骤S2中,所述层状氧化物、所述前驱体、所述分散剂的质量比为47~89∶1~3∶10~50。
10.根据权利要求7所述的钠离子电池正极材料的制备方法,其特征在于,所述分散剂包括乙二醇。
11.根据权利要求10所述的钠离子电池正极材料的制备方法,其特征在于,所述分散剂还包括选自乙醇、丁醇、丁二醇、戊醇、丙酮、甲乙酮、甲基异丁酮、环己酮、异佛尔酮、乙醚、四氢呋喃、1,4-二氧六环、戊烷、己烷、戊烯、己烯中一种或多种溶剂。
12.一种钠离子电池正极,其特征在于,包括集流体、导电剂、粘结剂及权利要求1至6任意一项所述的正极材料,所述集流体的至少一个表面上包含所述导电剂、所述粘结剂及所述正极材料。
13.一种钠离子电池,其特征在于,包括权利要求12所述的钠离子电池正极。
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