CN115911332A - Copper-manganese-based layered oxide material, preparation method, positive electrode and sodium ion battery - Google Patents
Copper-manganese-based layered oxide material, preparation method, positive electrode and sodium ion battery Download PDFInfo
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- CN115911332A CN115911332A CN202211633166.8A CN202211633166A CN115911332A CN 115911332 A CN115911332 A CN 115911332A CN 202211633166 A CN202211633166 A CN 202211633166A CN 115911332 A CN115911332 A CN 115911332A
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- manganese
- copper
- sodium
- oxide material
- layered oxide
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- 239000000463 material Substances 0.000 title claims abstract description 85
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 44
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011734 sodium Substances 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 16
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 46
- 239000002243 precursor Substances 0.000 claims description 35
- 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 30
- 229910052708 sodium Inorganic materials 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 20
- 239000007774 positive electrode material Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 150000001805 chlorine compounds Chemical class 0.000 claims description 9
- 150000002823 nitrates Chemical class 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 9
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 8
- 238000007580 dry-mixing Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 5
- 150000001860 citric acid derivatives Chemical class 0.000 claims description 5
- 150000003891 oxalate salts Chemical class 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- 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 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 5
- 229940039790 sodium oxalate Drugs 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007704 transition Effects 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 8
- 239000010405 anode material Substances 0.000 description 8
- 239000000661 sodium alginate Substances 0.000 description 8
- 235000010413 sodium alginate Nutrition 0.000 description 8
- 229940005550 sodium alginate Drugs 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000013543 active substance Substances 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229940071125 manganese acetate Drugs 0.000 description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-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
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000027455 binding Effects 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
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- 229940116318 copper carbonate Drugs 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
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- 239000010439 graphite Substances 0.000 description 2
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- 239000011656 manganese carbonate Substances 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 239000011564 manganese citrate Substances 0.000 description 2
- 235000014872 manganese citrate Nutrition 0.000 description 2
- 229940097206 manganese citrate Drugs 0.000 description 2
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
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- 150000003624 transition metals Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-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
- 230000002159 abnormal effect Effects 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- JQKUCPUQTWLCNU-UHFFFAOYSA-N copper;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Cu].OC(=O)CC(O)(C(O)=O)CC(O)=O JQKUCPUQTWLCNU-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 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 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
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- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a copper-manganese-based layered oxide material, a preparation method thereof, a positive electrode and a sodium ion battery, wherein the molecular general formula of the copper-manganese-based layered oxide material is Na x M y Cu a Mn 0.7 O 2+α Wherein M is one or more of alkali metal and alkaline earth metal elements, x is more than or equal to 0.75 and less than or equal to 1,0<y≤0.3，0<a is less than or equal to 0.3, alpha is more than or equal to-0.02 and less than or equal to 0.02, and the space group of the copper-manganese based layered oxide material is R3m. The copper-manganese-based layered oxide material according to the embodiment of the invention has a P3 phase (i.e., space group R3 m), and is empty relative to an O3 phaseThe gas is stable, and the rate performance is excellent; more Na was introduced relative to the P2 phase. The sodium ion secondary battery using the copper-manganese-based layered oxide material provided by the invention depends on the high activity of alkali metal or alkaline earth metal, the transition from divalent to trivalent copper and the transition from three-point quinquevalent to tetravalent manganese can realize higher first-cycle charge capacity and excellent cycle performance.
Description
Technical Field
The invention relates to the technical field of sodium-ion batteries, in particular to a copper-manganese-based layered oxide material, a preparation method thereof, a positive electrode and a sodium-ion battery.
Background
Due to the great increase of the price of lithium carbonate, the sodium ion battery becomes a hot point of research of various enterprises. At present, a great deal of literature reports electrode materials of sodium ion batteries, wherein the positive electrode material mainly comprises a layered oxide, a tunnel oxide, a polyanion compound, prussian blue/white and the like; there have also been material developments by various enterprises for the above four types of positive electrode materials.
Wherein, the layered oxide anode material obtains more attention by the advantages of simple synthesis process, high energy density and the like, the P2 phase (Na coordination environment is triangular prism, the stacking sequence of oxygen layers is 2, space group is P63/mmc or P63/mcm) NaTMO2 and O3 phase (Na coordination environment is octahedron, the stacking sequence of oxygen layers is 3, space group is
) Is currently the most studied material. Wherein, the O3 phase has high sodium content, high first cycle charge capacity, but poor electrochemical cycle performance, sensitivity to air and water and certain difficulty in application; the P2 phase has good stability in the electrochemical cycle process due to the large space of the sodium ions, and the sodium ions are rapidly deintercalated, but most of the P2 phase materials are unstable in the air and the first-cycle charge capacity of the P2 phase materials is generally low due to the low sodium content.
Disclosure of Invention
In order to solve the problems, the invention provides a copper-manganese-based layered oxide material with a P3 phase (a triangular prism in a Na coordination environment, a stacking sequence of oxygen layers of 3 and a space group of R3 m), a preparation method thereof, a positive electrode and a sodium ion battery, and aims to improve the air stability, the first-cycle charge capacity, the cycle performance and the rate capability of the material.
The invention provides a copper-manganese based layered oxide material in a first aspect.
The second aspect of the present invention provides a method for producing a copper-manganese-based layered oxide material.
A third aspect of the invention provides a positive electrode for a sodium-ion battery.
In a fourth aspect, the invention provides a sodium ion battery.
In order to solve the technical problem, the invention adopts the following technical scheme:
the copper-manganese-based layered oxide material according to the embodiment of the first aspect of the invention is used for a sodium-ion battery, and is characterized in that the molecular general formula of the copper-manganese-based layered oxide material is Na x M y Cu a Mn 0.7 O 2+α Wherein M is one or more of alkali metal and alkaline earth metal elements, x is more than or equal to 0.75 and less than or equal to 1,0<y≤0.3，0<a is less than or equal to 0.3, alpha is more than or equal to-0.02 and less than or equal to 0.02, and the space group of the copper-manganese based layered oxide material is R3m.
Further, M is any one or more selected from sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium.
Further, y + a =0.3.
The preparation method of the copper-manganese-based layered oxide material according to the embodiment of the second aspect of the invention comprises the following steps:
s1, weighing a sodium source, a copper source, a manganese source and an M metal source in proportion, wherein M in the M metal source is one or more of alkali metal and alkaline earth metal elements;
s2, fully mixing the sodium source, the copper source, the manganese source and the M metal source to obtain precursor powder;
and S3, sintering the precursor powder at the sintering temperature of 550-850 ℃ for 10-15h to obtain the copper-manganese-based layered oxide material.
Further, in the step S1,
the sodium source is selected from one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium acetate, sodium oxalate and sodium citrate;
the copper source, the manganese source and the M metal source are respectively selected from one or more of oxides, chlorides, nitrates, sulfates, carbonates, acetates, oxalates and citrates of all metals.
Further, in the step S1, the amount of the sodium source is 100-108wt% of the stoichiometric amount based on the sodium in the sodium source.
In step S2, the precursor powder is obtained by treating each raw material by any one of a dry mixing method, a spray drying method, a sol-gel method, or a coprecipitation method.
Further, in the step S3, the temperature rise rate during sintering is 3-5 ℃/min, and the sintering temperature is 700-800 ℃.
Further, the preparation method also comprises the following steps:
and S4, grinding and sieving the sintered powder to obtain copper-manganese-based layered oxide material powder.
According to an embodiment of the third aspect of the invention, the positive electrode includes:
a positive current collector;
the positive electrode active material layer is arranged on the surface of the positive electrode current collector and contains the copper-manganese-based layered oxide material according to any one of the embodiments of the first aspect.
Further, the positive electrode active material layer further contains a conductive agent and a binder.
Further, the conductive agent is selected from any one or more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
Further, any one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium alginate, sodium carboxymethylcellulose and styrene butadiene rubber is/are used as the binder.
A sodium-ion battery according to an embodiment of the fourth aspect of the invention comprises a positive electrode according to any of the embodiments of the third aspect.
The technical scheme of the invention at least has one of the following beneficial effects:
according to the embodiment of the invention, the space group of the copper-manganese-based layered oxide material is R3m, namely P3 phase, the Na coordination environment is triangular prism, the stacking sequence of the oxygen layers is 3, so that compared with the P2 phase (the Na coordination environment is triangular prism, the stacking sequence of the oxygen layers is 2, and the space group is P63/mmc or P63/mcm), the repulsion between adjacent transition metal layers is weaker, more Na ions can be introduced, the stability in the electrochemical cycle process is good, and the de-intercalation of the sodium ions is faster; compared with an O3 phase, the material is stable in air, has excellent rate capability and is beneficial to improving the charge capacity;
the sodium ion secondary battery using the copper-manganese-based layered oxide material provided by the invention depends on the high activity of alkali metal or alkaline earth metal, the transition from divalent to trivalent copper, and the transition from three-point quinquevalent to tetravalent manganese can realize higher first cycle charge capacity, excellent cycle performance and rate performance, and good air stability and safety are realized by using copper element, so that the sodium ion secondary battery has great practical value;
in addition, the preparation method provided by the embodiment of the invention has the advantages of simple preparation process, safe and nontoxic raw materials and low manufacturing cost.
Drawings
FIG. 1 is an XRD pattern of the copper manganese based layered oxide materials obtained at different sintering temperatures of examples 1-2 and comparative example;
FIG. 2 is an SEM image of the copper-manganese-based layered oxide material obtained in example 2;
FIG. 3 is a charge-discharge curve of the sodium ion batteries obtained in examples 1-2 and comparative example;
fig. 4 is a graph showing cycle performance of the sodium ion batteries obtained in examples 1 to 2 and comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention.
First, a copper manganese-based layered oxide material and a method for preparing the same according to an embodiment of the present invention will be specifically described.
For sodium ion batteries, which are one of the hot spots in current research, much research is currently conducted on the NaTMO of the P2 phase 2 NaTMO with O3 2 There is a problem that the electrochemical cycle performance and the first-cycle charge capacity cannot be compatible. In view of the above, the present inventors have found that the P3 phase copper-manganese-based layered oxide can be compatible with each other through extensive studies.
According to the first aspect of the invention, the provided copper-manganese-based layered oxide material is used for a sodium-ion battery, and the molecular formula of the copper-manganese-based layered oxide material is Na x M y Cu a Mn 0.7 O 2+α Wherein M is one or more of alkali metal and alkaline earth metal elements, x is more than or equal to 0.75 and less than or equal to 1,0<y≤0.3，0<a is less than or equal to 0.3, alpha is more than or equal to-0.02 and less than or equal to 0.02, and the space group of the copper-manganese based layered oxide material is R3m.
According to the copper-manganese-based layered oxide material disclosed by the embodiment of the invention, good air stability and safety are realized by using copper element, and by means of high activity of M metal (namely alkali metal or alkaline earth metal), divalent to trivalent copper is converted, and the valence change from three-point pentavalent to tetravalent manganese can realize higher first-cycle charge capacity, excellent cycle performance and rate performance. And no metal (such as Fe) causing material instability is introduced, and the cycling stability under high voltage can be realized. In addition, the space group of the copper-manganese-based layered oxide material is R3m, namely P3 phase, and more Na is introduced compared with P2 phase (the repulsion between the adjacent transition metal layers of P3 phase is weaker than that of P2 phase, so that more sodium ions can be accommodated), so that the stability in the electrochemical cycle process is better, and the charging capacity is further improved while the higher electrochemical cycle performance is maintained.
According to some embodiments of the invention, wherein M is any one or more selected from the group consisting of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium. The M metal is more preferably potassium, magnesium, calcium, or barium, in consideration of the combination of binding activity, economy, and abundance of resources.
Further, y + a =0.3. That is, 30at% of Mn is replaced by M together with Cu. The component proportion is favorable for further improving the stability of the composite material in the air, and simultaneously, the first-week charge capacity and the electrochemical cycle performance can be considered.
As an example, the copper manganese-based layered oxide material according to the present invention may include Na, for example 0.75 K 0.2 Mn 0.7 Cu 0.1 O 2 、Na 0.8 K 0.1 Mn 0.7 Cu 0.2 O 2 、Na 0.8 Mg 0.05 Mn 0.7 Cu 0.2 O 2 、Na 0.8 Mg 0.1 Mn 0.7 Cu 0.1 O 2 、Na 0.8 Mg 0.1 Mn 0.7 Cu 0.1 O 2 、Na 0.8 K 0.1 Mn 0.7 Cu 0.2 O 2 、Na 0.8 K 0.1 Mn 0.7 Cu 0.2 O 2 And the like. Of course, the above are merely examples, and the present invention is not limited thereto.
The following describes the above-described method for producing a copper-manganese-based layered oxide material, that is, the method for producing a copper-manganese-based layered oxide material according to an embodiment of the present invention.
The preparation method of the copper-manganese-based layered oxide material comprises the following steps:
s1, weighing a sodium source, a copper source, a manganese source and an M metal source in proportion, wherein M in the M metal source is one or more of alkali metal and alkaline earth metal elements.
That is, first, various starting materials were weighed.
The sodium source is selected from one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium acetate, sodium oxalate and sodium citrate;
the copper source, the manganese source and the M metal source are respectively selected from one or more of oxides, chlorides, nitrates, sulfates, carbonates, acetates, oxalates and citrates of all metals.
More specifically, as the copper source, for example, one or more of copper oxide (in the present invention, a generic name of copper oxide and cuprous oxide), copper chloride, copper nitrate, copper sulfate, copper carbonate, copper acetate, copper oxalate, copper citrate, and the like can be selected.
Similarly, as the manganese source, for example, one or more of manganese oxide (in the present invention, a general term of manganese monoxide and manganese dioxide), manganese chloride, manganese nitrate, manganese sulfate, manganese carbonate, manganese acetate, manganese oxalate, manganese citrate, and the like can be used.
The source of M metal may be selected from one or more of oxides, chlorides, nitrates, sulfates, carbonates, acetates, oxalates, citrates of alkali metals, and oxides, chlorides, nitrates, sulfates, carbonates, acetates, oxalates, citrates of alkaline earth metals.
The various raw materials can be appropriately selected according to a specific processing method (specifically, step S2 to be described later). The specific details will be further described later in conjunction with step S2.
Further, in some embodiments of the invention, the sodium source is used in an amount of 100 to 108wt% of the stoichiometric amount based on the sodium therein. That is, a slight excess of Na was used. This is because, considering that the Na source is partially lost during the alloying process, a slight excess amount of the Na source may be appropriately added in order to achieve a predetermined chemical composition. In addition, a slight excess of the sodium source helps to promote the formation of a stable P3 phase.
And S2, fully mixing the sodium source, the copper source, the manganese source and the M metal source to obtain precursor powder.
That is, the starting materials were weighed and then sufficiently mixed to obtain a precursor powder for producing a target copper-manganese-based layered oxide material.
In some embodiments of the present invention, the precursor powder may be obtained by treating each raw material by a dry mixing method, a spray drying method, a sol-gel method, or a coprecipitation method, for example.
Next, each processing method will be described.
(1) Dry mixing process
In the dry mixing method, the raw material powders are dry-mixed as they are without adding a solvent or a dispersion liquid thereto, and are dispersed by, for example, a ball mill method or a planetary mill to obtain a precursor powder.
For dry mixing treatment, the sodium source may be one or more selected from sodium carbonate, sodium acetate, sodium bicarbonate, sodium oxalate, or sodium citrate; as the copper source, for example, one or more of oxides, copper chloride, copper nitrate, copper sulfate, copper carbonate and the like can be used; the manganese source may be, for example, one or more of manganese oxide (which is a generic term for manganese monoxide and manganese dioxide in the present invention), manganese chloride, manganese nitrate, manganese sulfate, and manganese carbonate; the M metal source may be one or more selected from alkali metal oxides, chlorides, nitrates, sulfates, carbonates, and alkaline earth metal oxides, chlorides, nitrates, sulfates, and carbonates.
Specifically, the weighed powder and grinding balls are put into a ball milling tank for ball milling.
Wherein the mass ratio of the ball-milling mixed powder to the grinding balls is (1-50): 1. preferably, the powder-to-ball ratio is 3. By selecting a proper powder-ball ratio, the mixing effect can be improved, and sufficient surface energy is given to the powder in the ball milling process, so that the subsequent solid-phase sintering reaction is facilitated to be promoted.
The rotation speed is, for example, 200 to 1000rpm, preferably 400rpm. Appropriate rotation speeds may improve mixing efficiency.
The ball milling time is, for example, 1 to 24 hours, preferably 6 hours. The proper ball milling time can ensure the full mixing and improve the production efficiency.
Wherein the particle size of the precursor powder is 1-15 μm, preferably 1-10 μm. If the powder is too coarse, the powder is not beneficial to forming the anode active material powder by subsequent solid-phase sintering, and if the powder is too fine, the powder is easy to agglomerate, thereby affecting the uniformity.
(2) Spray drying method
That is, each raw material powder is dispersed in a dispersion to form a uniform slurry, and thereafter the slurry is subjected to spray drying to form a precursor powder.
Wherein, during the process of forming the slurry, for example, wet ball milling can be combined, so that the slurry is more stable and is more uniformly dispersed.
Further, in the wet ball milling, a certain dispersant such as PAA (polyacrylic acid), PMAA (polymethacrylic acid), and the like may also be incorporated.
Among them, water, ethanol, and the like can be used as the dispersion liquid. The use of ethanol for dispersion is preferred because it is less likely to cause re-agglomeration during the spray drying process.
Further, for the spray drying method, there is no particular requirement for each powder, and all of the above-mentioned raw material powders can be arbitrarily selected.
(3) Sol gel process
The sol-gel method is a method in which each raw material powder is first made into a sol in a solvent, then evaporated to dryness to form a precursor gel, and finally the precursor gel is degreased by heating to obtain a precursor powder.
Specifically, for example, each raw material powder may be dispersed in water or ethanol to form a precursor solution; adding appropriate amount of chelating agent such as citric acid, stirring at 50-100 deg.C, and evaporating the dispersion (i.e. water or ethanol) to obtain precursor gel; and finally, presintering for 1-4 hours at the temperature of 200-500 ℃ to obtain precursor powder.
Among them, for the sol-gel method, organic salts having a relatively larger molecular weight are preferable in order to be more stable in the process of forming a gel, thereby enabling better dispersion uniformity. Specifically, for example, the sodium source may be one or more selected from sodium carbonate, sodium bicarbonate, sodium oxalate, or sodium citrate; copper source, such as copper acetate, copper oxalate, citric acid copper or more; as the manganese source, similarly, for example, one or more of manganese acetate, manganese oxalate, manganese citrate, and the like; the metal source of M can be selected from one or more of acetate, oxalate and citrate of alkali metal and acetate, oxalate and citrate of alkaline earth metal.
(4) Coprecipitation method
The coprecipitation method is a method in which each raw powder except a sodium source is dissolved in a solvent, acetone is coprecipitated by adjusting the pH of the solution, and then the solution is mixed with the sodium source (for example, dry ball milling, etc.), thereby obtaining a precursor powder.
Specifically, for example, each raw material powder is dissolved in water to form a solution having a predetermined concentration; then, slowly dripping the solution into alkaline aqueous solution with certain concentration and pH value, such as ammonia water, by a peristaltic pump to generate coprecipitate; and then washing the coprecipitate with water, drying, and fully mixing with sodium source powder to obtain precursor powder.
Among them, for the sol-gel method, the sodium source is not limited, and any of the above-mentioned sodium sources can be appropriately selected. The other raw materials are preferably highly soluble, and specifically, the copper source may be one or more selected from copper chloride, copper nitrate, copper sulfate, and the like; the manganese source can be one or more of manganese chloride, manganese nitrate and manganese sulfate; the M metal source may be one or more of chlorides, nitrates, sulfates, carbonates of alkali metals, chlorides, nitrates, sulfates of alkaline earth metals, and the like.
And S3, sintering the precursor powder at the sintering temperature of 550-850 ℃ for 10-15h to obtain the copper-manganese-based layered oxide material.
That is, it is necessary to mix and obtain a precursor powder, and the precursor powder is subjected to solid-phase sintering to cause a solid-phase reaction, thereby producing a positive electrode active material that can be used as a sodium ion battery.
Wherein, in order to obtain stable P3 phase, the heating rate is preferably 3-5 ℃/min during sintering, and the sintering temperature is preferably 700-800 ℃.
The proper temperature rise rate is beneficial to the full release of the by-products generated by the thermal decomposition reaction of the precursor powder, and the proper sintering temperature and the proper heat preservation time are beneficial to controlling the crystalline phase and being suitable for the growth of the crystal grains without abnormal growth.
In addition, in order to facilitate further forming a slurry with good dispersibility to be coated on the positive electrode current collector, the preparation method preferably further comprises the following steps:
and S4, grinding and sieving the sintered powder to obtain copper-manganese based layered oxide material powder.
Thus, the copper-manganese-based layered oxide material powder according to the present invention can be prepared.
Next, a positive electrode obtained using the above copper-manganese-based layered oxide material is described.
The positive electrode according to an embodiment of the present invention includes:
a positive current collector;
the positive electrode active material layer is arranged on the surface of the positive electrode current collector and contains the copper-manganese-based layered oxide material in any one of the embodiments.
Further, the positive electrode active material layer further contains a conductive agent and a binder. Among them, the conductive agent can improve its conductivity, and the binder helps to improve the bonding strength between the positive active material layer and the positive current collector.
Specifically, the conductive agent is selected from any one or more of conductive carbon black, conductive graphite, carbon nanotubes, carbon fibers and graphene.
In addition, the binder is any one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), sodium Alginate (SA), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR).
One or more of PVDF, PTFE, sodium alginate, CMC and SBR are selected as the binder, so that the interface contact performance and the battery performance of the positive active material layer and the positive current collector can be further improved.
Specifically, PVDF has a high dielectric constant, good chemical stability and temperature characteristics, and has a positive effect of improving the adhesion between the positive active material layer and the positive current collector.
PTFE is a high molecular chemical material containing polytetrafluoroethylene. Polytetrafluoroethylene is produced by radical polymerization of tetrafluoroethylene. The polytetrafluoroethylene PTFE has the advantages of high temperature resistance (the working temperature is up to 250 ℃), low temperature resistance (5 percent of elongation can be kept even if the temperature is reduced to-196 ℃), corrosion resistance (inertia to most chemicals and solvents, strong acid and alkali resistance, water and various organic solvents resistance), and the like.
Sodium Alginate (SA) was used as a binder to form metal ion-coordinated sodium alginate on the surface of metal fluoride particles during electrode fabrication, successfully inhibiting dissolution into the layered oxide material. Namely, the copper-manganese-based layered oxide can be crosslinked with the SA adhesive in situ to form a conformal complex layer on the surface of the copper-manganese-based layered oxide particles, so that the dissolution of metal ions in the copper-manganese-based layered oxide in electrolyte can be effectively inhibited, and the reversibility of the anode is enhanced.
CMC is widely used as a binder of a negative electrode material of an aqueous system, and can obtain larger battery capacity, improve the cycle life of the battery and reduce the internal resistance of the battery.
The SBR binder has high binding strength, good mechanical stability and operability, is used as a binder in the battery industry, and has good binding effect and stable quality.
With respect to the method of providing the positive electrode active material layer on the surface of the positive electrode collector, there is no particular limitation, and for example, may include:
the copper-manganese-based layered oxide material may be prepared by dispersing 60 to 100 parts by mass, 0 to 10 parts by mass of a conductive agent, and 0 to 10 parts by mass of a binder in a solvent (for example, water, methanol, ethanol, or the like) to form a positive electrode slurry, and then coating the positive electrode slurry on the surface of a positive electrode current collector.
The positive electrode obtained as described above can be used to form a sodium ion battery.
The preparation of the copper-manganese-based layered oxide material, the positive electrode, and the sodium ion battery according to the present invention are further illustrated by examples below.
Example 1
(1) Preparation of copper-manganese-based layered oxide material Na0.75K0.2Mn0.7Cu0.1O2
The copper-manganese-based layered oxide material is prepared by a dry mixing method. The method specifically comprises the following steps:
mixing Na 2 CO 3 (analytical purity), K 2 CO 3 (analytically pure), cuO, mn 2 O 3 Mixing according to a molar ratio of 0.375; adding ethanol solvent, ball milling for 5 hr, oven drying to obtain precursor mixed powder, placing in muffle furnace, and treating at 700 deg.C for 12 hr to obtain black powder of layered oxide material Na0.75K0.2Mn0.7Cu0.1O2, with XRD spectrum shown in (a) of FIG. 1. From the XRD pattern, it was confirmed that the crystal structure of Na0.75K0.2Mn0.7Cu0.1O2 was an oxide having a P3 phase layered structure.
(2) Preparation of sodium ion battery
The copper-manganese-based layered oxide material prepared by the method is used for preparing a sodium ion battery as an active substance of a battery anode material, and the method comprises the following specific steps:
mixing the prepared Na0.75K0.2Mn0.7Cu0.1O2 powder with acetylene black and a binder polyvinylidene fluoride (PVDF) according to the weight ratio of 80:10:10, adding a proper amount of N-methyl pyrrolidone (NMP) solution, grinding in a normal-temperature drying environment to form slurry, then uniformly coating the slurry on a current collector aluminum foil, drying under an infrared lamp, and cutting into (8 multiplied by 8) mm2 pole pieces. Drying the pole piece for 10h at 110 ℃ under vacuum condition, and then transferring the pole piece to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaClO 4/diethyl carbonate (EC: DEC) solution as the electrolyte, to assemble a CR2032 button cell.
The charge and discharge test was performed at a current density of C/10 using a constant current charge and discharge mode. The test results are shown in fig. 3 and 4, respectively, under the conditions of a discharge cut-off voltage of 1.5V and a charge cut-off voltage of 4.5V. As can be seen from the figure, the first-cycle specific discharge capacity can reach 187.2mAh/g, the first-cycle coulombic efficiency is about 95%, and the capacity retention rate is 74.9% after 100 cycles of circulation.
Example 2
(1) Preparation of copper-manganese based layered oxide material Na0.8K0.1Mn0.7Cu0.2O2
The preparation process is the same as that of example 1, but the starting material is NaHCO 3 (analytically pure), KHCO 3 (analytically pure), manganese acetate and copper acetate, and the component ratio is different from that of example 1, wherein the molar ratio of each component in the example is 0.8.
Further, the heat treatment was carried out at 800 ℃ for 10 hours to obtain a black powder in which the layered oxide material was Na0.8K0.1Mn0.7Cu0.2O2. The XRD pattern of the compound is shown in (b) of figure 1. From the XRD pattern, it was confirmed that the crystal structure of Na0.8K0.1Mn0.7Cu0.2O2 was still an oxide having a P3 phase layered structure.
Fig. 2 is a Scanning Electron Microscope (SEM) image thereof, and it can be seen from fig. 2 that the material is in a plate shape and the particle size distribution is mainly from 1 to 10 microns.
(2) Preparation of sodium ion Battery
The prepared copper-manganese-based layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 1.
The test voltage ranges from 1.5 to 4.5V, and the test results are shown in FIGS. 3 and 4. As can be seen from the figure, the first-cycle specific discharge capacity can reach 213.8mAh/g, the first-cycle coulombic efficiency is about 95%, and the capacity retention rate is 80.68% after 100 cycles.
Example 3
(1) Preparation of copper-manganese based layered oxide material Na0.8Mg0.05Mn0.7Cu0.2O2
The preparation process is the same as that in example 1, but the starting materials are sodium acetate (analytically pure) and MgCO 3 (analytically pure), cuO, mn 2 O 3 And the component ratio of each component is different from that of the embodiment 1, and the molar ratio of each component in the embodiment is 0.4.
The layered oxide material of the obtained black powder was na0.8mg0.05mn0.7cu0.2o2. The XRD pattern is similar to that of example 1, and the detailed illustration and description thereof are omitted.
(2) Preparation of sodium ion battery
The copper-manganese-based layered oxide material prepared by the method is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 1. The test voltage range is 1.5-4.5V, the first-cycle specific discharge capacity can reach 193.2mAh/g, the first-cycle coulombic efficiency is about 95%, and the capacity retention rate is 79.54% after 100 cycles.
Example 4
(1) Preparation of copper-manganese based layered oxide material Na0.8Mg0.1Mn0.7Cu0.1O2
The preparation process is the same as that of example 2, but the starting material is NaHCO 3 (analytical grade), magnesium acetate (analytical grade), copper acetate, manganese acetate, and the component ratios are different from example 2, in this example, the molar ratio of each component is 0.8.
(2) Preparation of sodium ion battery
The prepared copper-manganese-based layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method were the same as in example 1. The test voltage range is 1.5-4.5V, the first-cycle specific discharge capacity can reach 215.2mAh/g, the first-cycle coulombic efficiency is about 95%, and the capacity retention rate is 83.24% after 100 cycles.
Example 5
(1) Preparation of copper-manganese based layered oxide material Na0.8Mg0.1Mn0.7Cu0.1O2
In this embodiment, a spray drying method is used to prepare precursor powder.
Specifically, sodium nitrate, potassium nitrate, copper nitrate and manganese acetate precursors are weighed according to a molar ratio of 0.8.1; placing the solution in a spray dryer, and performing spray drying at 130 ℃; the precursor after being sprayed and dried is collected and transferred into an aluminum oxide crucible, and the precursor is treated for 6 hours at 700 ℃ in a muffle furnace under the air atmosphere, so that the dark brown powder copper-manganese-based layered oxide material is Na0.8Mg0.1Mn0.7Cu0.1O2, and the XRD spectrum of the dark brown powder copper-manganese-based layered oxide material is similar to that in figure 1.
(2) Preparation of sodium ion battery
The copper-manganese-based layered oxide material prepared by the method is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method are the same as in example 1. The test voltage range is 1.5-4.5V, the first-cycle discharge specific capacity can reach 185.6mAh/g, the first-cycle coulombic efficiency is about 95%, and the capacity retention rate is 72.4% after 100 cycles of circulation.
Example 6
(1) Preparation of copper-manganese based layered oxide material Na0.8K0.1Mn0.7Cu0.2O2
In this embodiment, a sol-gel method is used to prepare precursor powder.
Specifically, firstly, precursor compounds of sodium sulfate, potassium sulfate, copper sulfate and manganese sulfate are weighed according to a molar ratio of 0.4 to 0.05 of; transferring the dried gel obtained by evaporation to an aluminum oxide crucible, and pre-burning for 2h at 200 ℃; and then the copper-manganese-based layered oxide material of the red brown black powder is obtained by heat treatment for 10 hours at 800 ℃ in a muffle furnace under the air atmosphere, the copper-manganese-based layered oxide material is Na0.8K0.1Mn0.7Cu0.2O2, and the XRD spectrum of the copper-manganese-based layered oxide material is similar to that of figure 1.
(2) Preparation of sodium ion battery
The prepared copper-manganese-based layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method are the same as in example 1. The test voltage range is 1.5-4.5V, the first-cycle specific discharge capacity can reach 210.2mAh/g, the first-cycle coulombic efficiency is about 95%, and the capacity retention rate is 78.4% after 100 cycles of circulation.
Example 7
(1) Preparation of copper-manganese-based layered oxide material
In this example, a coprecipitation method was used to prepare precursor powder.
Specifically, potassium acetate, copper acetate and manganese acetate precursors are weighed according to a molar ratio of 0.05; slowly dripping the prepared aqueous solution of potassium acetate, copper acetate and manganese acetate into an ammonia water solution with certain concentration and pH value by using a peristaltic pump tube; after the reaction is finished, taking out the generated precipitate, washing the precipitate with deionized water, and drying the precipitate in a vacuum oven at 80 ℃; uniformly mixing the dried powder and sodium hydroxide according to a stoichiometric ratio to obtain a precursor; and then transferring the precursor into a muffle furnace for heat treatment at 800 ℃ for 12h. And grinding the powder after the heat treatment to obtain a black copper-manganese based layered oxide material Na0.8K0.1Mn0.7Cu0.2O2, wherein an XRD pattern of the black copper-manganese based layered oxide material is similar to that in figure 1.
(2) Preparation of sodium ion battery
The prepared copper-manganese-based layered oxide material is used as an active substance of a battery anode material for preparing a sodium ion battery, and an electrochemical charge and discharge test is carried out. The procedure and test method are the same as in example 1. The test voltage range is 1.5-4.5V, the first-cycle specific discharge capacity can reach 215.3mAh/g, the first-cycle coulombic efficiency is about 95%, and the capacity retention rate is 82.3% after 100 cycles of circulation.
Comparative example
The same as example 1 except that the final sintering temperature for the powder was different from that of example 1.
In the comparative example, the sintering temperature was 900 ℃.
As can be seen from (c) in fig. 1, at this high temperature sintering, the P2 phase has been converted.
In addition, fig. 3 and 4 show the electrical property test results of the comparative example. As can be seen from fig. 3 and 4, the specific discharge capacity at the first cycle and the electrical cycle performance are significantly lower than those of the sodium ion battery of the embodiment of the present application.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A copper-manganese based layered oxide material for a sodium ion battery, characterized in that the copper-manganese based layer isThe molecular general formula of the oxide-like material is Na x M y Cu a Mn 0.7 O 2+α Wherein M is one or more of alkali metal and alkaline earth metal elements, x is more than or equal to 0.75 and less than or equal to 1,0<y≤0.3，0<a is less than or equal to 0.3, and alpha is more than or equal to-0.02 and less than or equal to 0.02,
the space group of the copper-manganese-based layered oxide material is R3m.
2. The copper-manganese based layered oxide material according to claim 1, wherein M is any one or more selected from the group consisting of sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium.
3. The copper-manganese based layered oxide material according to claim 1, wherein y + a =0.3.
4. A method for producing a copper-manganese-based layered oxide material according to any one of claims 1 to 3, characterized by comprising the steps of:
s1, weighing a sodium source, a copper source, a manganese source and an M metal source in proportion, wherein M in the M metal source is one or more of alkali metal and alkaline earth metal elements;
s2, fully mixing the sodium source, the copper source, the manganese source and the M metal source to obtain precursor powder;
and S3, sintering the precursor powder at the sintering temperature of 550-850 ℃ for 10-15h to obtain the copper-manganese-based layered oxide material.
5. The method according to claim 4, wherein in the step S1,
the sodium source is selected from one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium acetate, sodium oxalate and sodium citrate;
the copper source, the manganese source and the M metal source are respectively selected from one or more of oxides, chlorides, nitrates, sulfates, carbonates, acetates, oxalates and citrates of all metals.
6. The method according to claim 4, wherein the sodium source is used in an amount of 100 to 108wt% based on the sodium in the sodium source in step S1.
7. The method according to claim 4, wherein in step S2, the precursor powder is obtained by treating each raw material by any one of a dry mixing method, a spray drying method, a sol-gel method, or a coprecipitation method.
8. The production method according to claim 4, wherein in the step S3, the temperature rise rate at the time of sintering is 3 to 5 ℃/min, and the sintering temperature is 700 to 800 ℃.
9. The method of claim 4, further comprising the steps of:
and S4, grinding and sieving the sintered powder to obtain copper-manganese-based layered oxide material powder.
10. A positive electrode, comprising:
a positive current collector;
the positive electrode active material layer is arranged on the surface of the positive electrode current collector, and the positive electrode active material layer contains the copper-manganese-based layered oxide material disclosed by any one of claims 1 to 3 or the copper-manganese-based layered oxide material prepared by the preparation method disclosed by any one of claims 4 to 9.
11. A sodium ion battery comprising the positive electrode according to claim 10.
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| CN118016864A (en) * | 2024-04-10 | 2024-05-10 | 深圳市贝特瑞新能源技术研究院有限公司 | Layered oxide positive electrode material and preparation method and application thereof |
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| CN116190633A (en) * | 2023-05-05 | 2023-05-30 | 北京中科海钠科技有限责任公司 | Layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application |
| CN116190633B (en) * | 2023-05-05 | 2023-09-19 | 北京中科海钠科技有限责任公司 | Layered oxide positive electrode material, preparation method thereof, positive electrode composition, sodium ion secondary battery and application |
| CN118016864A (en) * | 2024-04-10 | 2024-05-10 | 深圳市贝特瑞新能源技术研究院有限公司 | Layered oxide positive electrode material and preparation method and application thereof |
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