CN116825991A - Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery - Google Patents
Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery Download PDFInfo
- Publication number
- CN116825991A CN116825991A CN202310787267.9A CN202310787267A CN116825991A CN 116825991 A CN116825991 A CN 116825991A CN 202310787267 A CN202310787267 A CN 202310787267A CN 116825991 A CN116825991 A CN 116825991A
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- CN
- China
- Prior art keywords
- ion battery
- sodium ion
- positive electrode
- electrode material
- sodium
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 169
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000011734 sodium Substances 0.000 claims abstract description 81
- 239000002105 nanoparticle Substances 0.000 claims abstract description 53
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 32
- 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 abstract description 31
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 17
- 238000001338 self-assembly Methods 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 83
- 238000010438 heat treatment Methods 0.000 claims description 39
- 229910052748 manganese Inorganic materials 0.000 claims description 38
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 35
- 230000005855 radiation Effects 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 238000005245 sintering Methods 0.000 claims description 24
- 239000012467 final product Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 230000002441 reversible effect Effects 0.000 abstract 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 27
- 229910001437 manganese ion Inorganic materials 0.000 description 23
- 239000010405 anode material Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- 239000010949 copper Substances 0.000 description 18
- 239000003792 electrolyte Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000006183 anode active material Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 12
- 239000006256 anode slurry Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000011656 manganese carbonate Substances 0.000 description 11
- 235000006748 manganese carbonate Nutrition 0.000 description 11
- 229940093474 manganese carbonate Drugs 0.000 description 11
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 11
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000011135 tin Substances 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 229910021385 hard carbon Inorganic materials 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000012716 precipitator Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 229940099596 manganese sulfate Drugs 0.000 description 6
- 239000011702 manganese sulphate Substances 0.000 description 6
- 235000007079 manganese sulphate Nutrition 0.000 description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 6
- 239000010955 niobium Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- -1 sodium transition metal Chemical class 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 229940116318 copper carbonate Drugs 0.000 description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229940118662 aluminum carbonate Drugs 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 229940062993 ferrous oxalate Drugs 0.000 description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- WYGQZDSIRBBVTA-UHFFFAOYSA-D [Nb+5].[Nb+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O Chemical compound [Nb+5].[Nb+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WYGQZDSIRBBVTA-UHFFFAOYSA-D 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 238000002065 inelastic X-ray scattering Methods 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [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
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 230000002427 irreversible effect Effects 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- HBTFASPVVFSRRI-UHFFFAOYSA-N manganese(2+);dinitrate;hydrate Chemical compound O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O HBTFASPVVFSRRI-UHFFFAOYSA-N 0.000 description 1
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention relates to the technical field of sodium ion batteries, and particularly provides a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery. The shape of the positive electrode material of the sodium ion battery is a hollow sphere and/or spheroid; the wall body of the positive electrode material of the sodium ion battery has a porous structure; the positive electrode material of the sodium ion battery is formed by self-assembly of nano particles; the nano particles are layered sodium transition metal oxides. The positive electrode material of the sodium ion battery has higher reversible oxygen activity, structural stability and multiplying power discharge capacity, so that when the positive electrode material of the sodium ion battery is used as the positive electrode material of the sodium ion battery and assembled into the sodium ion battery, the energy density, specific capacity, multiplying power performance and cycle performance of the battery can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery positive electrode material, a preparation method thereof and a sodium ion battery.
Background
The requirements of electric vehicles and energy storage for energy storage devices make the requirements of lithium ion batteries explosive growth, resulting in excessive prices of lithium ion batteries, and therefore products capable of replacing lithium ion batteries in the fields of electric vehicle batteries and large-scale energy storage are required to be searched. Among the many new batteries replacing lithium ion batteries, sodium ion batteries are more competitive and promising for applications in low-speed electric vehicles and large-scale energy storage systems than lithium ion batteries due to their lower cost. Compared to Li, na has a higher mass and standard redox potential, resulting in a lower energy density for sodium ion cells than for lithium ion cells. Today, the energy density of sodium ion battery cells is close to 150Wh/kg, far lower than that of lithium ion battery cells (up to 300 Wh/kg), and the price advantage is therefore also under debate. In addition, na + Compared with Li + The radius is larger, and the stress generated in the active material is more remarkable in the service process, so that irreversible volume change is brought, and the cycle life and the multiplying power performance of the sodium ion battery are far lower than those of the lithium ion battery.
The current positive electrode material of the sodium ion battery mainly comprises polyanion compounds, prussian blue compounds and layered transition metal oxide Na x TMO 2 (TM is mainly transition metal such as Mn, ni and Fe). Layered sodium transition metal oxide Na x TMO 2 The high specific capacity is realized, so that the composite material is one of the most promising positive electrode materials in the sodium ion battery research field. Traditional layered sodium transition metal oxide crystals are mainly divided into two types of P2 and O3 according to the difference of sodium ion occupation, and the crystals have a P2 structure when Na ions occupy the positions of prisms; and when Na ions occupy octahedral vacancies, the structure is O3. Compared with the O3 structural material, the P2 structural material has fast diffusion of sodium ions in a matrix and good stability to air and water, so that the material is favored by academia and enterprises. However, the P2 structure material has the disadvantage of lower specific capacity and energy density in the use process of the full cell assembled with hard carbon.
As can be seen from the above, at present, layered sodium transition metal oxidation Na of the substance x TMO 2 High specific capacity, long-cycle stability and excellent rate discharge capability cannot be considered.
Disclosure of Invention
Aiming at the problem that the existing sodium ion battery anode material still cannot achieve high specific capacity, long-cycle stability and excellent multiplying power discharge capacity, the invention provides a sodium ion battery anode material, a preparation method thereof and a sodium ion battery.
In order to achieve the above object, the present invention has the following technical scheme:
a sodium ion battery anode material, wherein the shape of the sodium ion battery anode material is hollow sphere and/or spheroid; the wall body of the positive electrode material of the sodium ion battery is provided with a porous structure;
the positive electrode material of the sodium ion battery is formed by self-assembly of nano particles;
the nano particles are layered sodium transition metal oxides.
Further, the sodium ion battery positive electrode material further comprises at least one of the following technical characteristics:
(1) The average diameter of the positive electrode material of the sodium ion battery is 1-10 mu m;
(2) The average particle diameter of the nano particles is 60 nm-200 nm;
(3) The layered sodium transition metal oxide has the general formula:
(Na 1-x A x )(Mn 1-y M y )O 2 ；
wherein A is at least one selected from K, mg, ca, al;
M is selected from at least one of Li, cu, sn, Y, nb, mg, ni, fe, zn, ti, co, al;
0<x≤0.2；0≤y≤0.5；
(4) The porous structure is formed by mutually stacking and enclosing adjacent nano particles in the same positive electrode material particles of the sodium ion battery;
(5) The crystal structure of the layered sodium transition metal oxide is O3 phase.
Further toThe nanoparticle comprises (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 Nanoparticles, (Na) 0.90 Mg 0.10 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 Nanoparticles, (Na) 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 Nanoparticles, (Na) 0.8 K 0.2 )(Mn 0.8 Mg 0.16 Nb 0.04 )O 2 Nanoparticles, (Na) 0.95 Al 0.05 )(Mn 0.6 Ti 0.35 Y 0.05 )O 2 At least one of the nanoparticles.
Compared with the prior art, the sodium ion battery anode material provided by the embodiment of the invention has the advantages that as the shape of the sodium ion battery anode material is hollow sphere and/or spheroid, the wall body of the sodium ion battery anode material has a porous structure, and the sodium ion battery anode material is formed by self-assembling layered sodium transition metal oxide nano particles, wherein the layered sodium transition metal oxide can activate the anion redox activity, and the specific capacity and the cycle stability of the material are effectively increased; because the shape of the positive electrode material of the sodium ion battery is hollow sphere and/or spheroid, and the wall body is provided with a porous structure, the hollow inside the positive electrode material is communicated with the outside through the porous structure, so that the stress generated by volume deformation of the positive electrode material of the sodium ion battery in the use process can be effectively released, even effectively eliminated, and the multiplying power discharging capacity of the material can be simultaneously considered, therefore, when the positive electrode material is assembled into the sodium ion battery, the energy density, the specific capacity, the multiplying power performance and the cycle performance of the battery can be effectively improved.
Correspondingly, the preparation method of the sodium ion battery anode material comprises the following steps:
mixing a salt solution containing a manganese source with a precipitant, and precipitating by adopting a precipitation method to obtain a manganese-containing precursor;
mixing an M-containing compound with the manganese-containing precursor according to the stoichiometric ratio of the final product, and performing first heat treatment to obtain an oxide precursor;
mixing a sodium-containing compound, an A-containing compound and the oxide precursor according to the stoichiometric ratio of the final product, and performing second heat treatment to obtain the final product;
wherein M is selected from at least one of Li, cu, sn, Y, nb, mg, ni, fe, zn, ti, co, al;
a is selected from at least one of K, mg, ca, al.
Further, the salt solution is selected from at least one of manganese-containing sulfate and hydrate thereof, manganese-containing nitrate and hydrate thereof, manganese-containing chloride and hydrate thereof.
Further, the precipitant is at least one selected from sodium hydroxide, sodium carbonate and sodium bicarbonate; the usage amount of the precipitant at least ensures that manganese in the salt solution is completely precipitated;
the M-containing compound is at least one selected from the group consisting of an oxide of M, a hydroxide of M and a carbonate of M.
Further, the first heat treatment is selected from microwave radiation or resistive heating;
the microwave radiation condition is that sintering is carried out for 10min to 1h at the constant temperature of 300 to 600 ℃;
the resistance heating condition is that sintering is carried out for 1h to 5h at the constant temperature of 300 ℃ to 600 ℃.
Further, the sodium-containing compound is selected from at least one of sodium carbonate and sodium hydroxide;
the compound containing A is at least one selected from carbonate containing A and hydroxide containing A.
Further, the second heat treatment is selected from microwave radiation or a combination of microwave radiation and resistive heating;
the microwave radiation condition is that the constant temperature sintering is carried out for 10min to 1h at 300 to 600 ℃, and then the constant temperature sintering is carried out for 1 to 3h at 700 to 1000 ℃;
the combination of microwave radiation and resistance heating is that resistance heating is adopted to sinter for 1-5 hours at a constant temperature of 300-600 ℃, then microwave radiation is adopted to heat up to 700-1000 ℃ and sinter for 1-3 hours at a constant temperature.
Compared with the prior art, the preparation method of the sodium ion battery anode material provided by the embodiment of the invention prepares the sphere precursor in a precipitation mode, and the sodium ion battery anode material can be obtained through two heat treatments.
And the sodium ion battery comprises a positive electrode active layer, wherein the positive electrode active layer contains the sodium ion battery positive electrode material or contains the sodium ion battery positive electrode material prepared by the sodium ion battery positive electrode material preparation method.
Compared with the prior art, the sodium ion battery provided by the embodiment of the invention effectively solves the problem of the traditional layered sodium transition metal oxide Na because the active substance of the positive electrode is the positive electrode material of the sodium ion battery provided by the invention x TMO 2 The problems of high specific capacity, long-cycle stability and excellent multiplying power discharge capacity can not be considered, so that the sodium ion battery has higher practicability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a positive electrode material of a sodium ion battery prepared in example 1;
FIG. 2 is an SEM image of the positive electrode material of the sodium ion battery prepared in example 1;
FIG. 3 is an XRD pattern of the positive electrode material of the sodium ion battery prepared in example 2;
FIG. 4 is an XRD pattern of the positive electrode material of the sodium ion battery prepared in example 3;
FIG. 5 is an SEM image of the positive electrode material of a sodium ion battery prepared in example 7;
fig. 6 is a graph of the OK edge map of the resonance inelastic X-ray scattering for the sodium ion batteries of application example 1 and comparative example 1, comparative example 2 charged to 4.5V, respectively.
Fig. 7 is a graph showing the cycle performance of the sodium ion battery of application example 1 and comparative example 1;
fig. 8 is a graph showing the ratio performance of the sodium ion battery of application example 1 and comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In one aspect of the invention, a positive electrode material of a sodium ion battery is provided, and the positive electrode material of the sodium ion battery is hollow spheres and/or spheroids; the wall body of the positive electrode material of the sodium ion battery is provided with a porous structure; the positive electrode material of the sodium ion battery is formed by self-assembly of nano particles; the nano particles are layered sodium transition metal oxides.
Because the positive electrode material of the sodium ion battery is provided with the hollow sphere and/or spheroid, and the wall body is provided with the porous structure, the hollow inside the positive electrode material is communicated with the outside through the porous structure, so that the stress generated by the volume deformation of the positive electrode material of the sodium ion battery in the use process can be effectively released, and even effectively eliminated.
In some embodiments, the average particle size of the nano particles is 60 nm-200 nm, and the nano particles are in the particle size range, so that the sodium ion battery positive electrode material is formed by self-assembly, each sodium ion battery positive electrode material has higher stacking density and compaction density, the structural strength of the interior of the sodium ion battery positive electrode material is improved, and the risk of collapse of the sodium ion battery positive electrode material due to volume deformation in the charging and discharging processes is effectively inhibited. In some embodiments, the porous structure in the same positive electrode material of the sodium ion battery is formed by mutually stacking and enclosing adjacent nano particles, so that rapid diffusion of sodium ions is facilitated.
In some embodiments, the crystal structure of the layered sodium transition metal oxide is an O3 phase, and since the sodium ion battery positive electrode material is formed by stacking a plurality of nanoparticles, and the nanoparticles form a porous structure in the process of stacking each other, the hollow part inside the sodium ion battery material can be communicated with the outside through the porous structure, and the diffusion effect of sodium ions in the O3 phase is improved from a macroscopic level.
In some embodiments, the layered sodium transition metal oxide has the general formula:
(Na 1-x A x )(Mn 1-y M y )O 2 ；
wherein A is at least one selected from K, mg, ca, al; m is selected from at least one of Li, cu, sn, Y, nb, mg, ni, fe, zn, ti, co, al; x is more than 0 and less than or equal to 0.2; y is more than or equal to 0 and less than or equal to 0.5; in the layered sodium transition metal oxide, as A is doped into sodium, electrochemical activities of oxygen anions are excited to different degrees, so that specific capacity is contributed to the sodium ion battery anode material, more specific capacity can be released by the sodium ion battery anode material, and energy density is improved.
In some embodiments, the average diameter of the positive electrode materials of the sodium ion battery is between 1 μm and 10 μm, and the average diameter of the positive electrode materials of the sodium ion battery is in the range, so that the positive electrode materials of the sodium ion battery are all micron-sized particles, the stacking density among the positive electrode materials of the sodium ion battery can be effectively improved, and the tap density is improved.
In some embodiments, the sodium ion battery positive electrode material consists of (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 Nanoparticles, (Na) 0.90 Mg 0.10 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 Nanoparticles, (Na) 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 Nanoparticles, (Na) 0.8 K 0.2 )(Mn 0.8 Mg 0.16 Nb 0.04 )O 2 Nanoparticles, (Na) 0.95 Al 0.05 )(Mn 0.6 Ti 0.35 Y 0.05 )O 2 At least one of the nano particles is assembled, and the morphology of the assembled positive electrode material of the sodium ion battery is at least one of hollow spheres and spheroids. For example, the sodium ion battery positive electrode material may be a material consisting of (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 The nanoparticles are self-assembled, and may be formed from (Na 0.90 Mg 0.10 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 Nanoparticles self-assemble or are formed from (Na 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 Nanoparticles self-assemble or are formed from (Na 0.8 K 0.2 )(Mn 0.8 Mg 0.16 Nb 0.04 )O 2 Nanoparticles self-assembled, or (Na 0.95 Al 0.05 )(Mn 0.6 Ti 0.35 Y 0.05 )O 2 Nanoparticles self-assemble or are formed from (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 Nanoparticle sum (Na) 0.90 Mg 0.10 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 The nanoparticles are either self-assembled by mixing both or are formed from (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 Nanoparticles, (Na) 0.90 Mg 0.10 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 Nanoparticle (Na) 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 The nano particles are mixed and self-assembled, or are formed by (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 Nanoparticles, (Na) 0.90 Mg 0.10 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 Nanoparticles, (Na) 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 Nanoparticle (Na) 0.8 K 0.2 )(Mn 0.8 Mg 0.16 Nb 0.04 )O 2 Nanoparticles the four nanoparticles are mixed and self-assembled, and so on. These several kinds of nanoThe positive electrode material of the sodium ion battery assembled by the rice particles can effectively increase the specific capacity and the cycling stability of the material. Because the assembled positive electrode material of the sodium ion battery is a hollow sphere and/or spheroid micron-sized material, the increase of stress caused by volume deformation in the charge and discharge process can be effectively inhibited, and the multiplying power discharge capacity of the material is effectively considered, so that the energy density, specific capacity, multiplying power performance and cycle performance of the sodium ion battery can be effectively improved when the assembled positive electrode material of the sodium ion battery is assembled into the sodium ion battery.
Based on the sodium ion battery positive electrode material, a second aspect of the invention provides a preparation method of the sodium ion battery positive electrode material.
Specifically, the preparation method of the positive electrode material of the sodium ion battery comprises the following steps:
and step S01, mixing a salt solution containing a manganese source with a precipitant, and precipitating by adopting a precipitation method to obtain a manganese-containing precursor.
And step S02, mixing an M-containing compound with the manganese-containing precursor according to the stoichiometric ratio of the final product, and performing first heat treatment to obtain an oxide precursor, wherein M is at least one selected from Li, cu, sn, Y, nb, mg, ni, fe, zn, ti, co, al.
S03, carrying out mixing treatment on the sodium-containing compound, the A-containing compound and the oxide precursor according to the stoichiometric ratio of the final product, and carrying out second heat treatment to obtain the final product; wherein A is at least one selected from K, mg, ca, al.
The preparation method is explained in detail below.
In step S01, a salt solution containing a manganese source is referred to, and the manganese source is a soluble manganese source, for example, in the form of manganese ions, so that the manganese ions are present in the salt solution, which is advantageous for the reaction. In some embodiments, the salt containing a manganese source is selected from at least one of manganese-containing sulfate and its hydrates, manganese-containing nitrate and its hydrates, manganese-containing chloride and its hydrates, such as at least one of manganese sulfate, manganese sulfate hydrate, manganese nitrate hydrate, manganese chlorate hydrate. In some embodiments, the precipitant is at least one selected from sodium hydroxide, sodium carbonate and sodium bicarbonate, and the main purpose of the precipitant is to completely precipitate the manganese source (i.e. manganese ions), so that the manganese source is fully utilized in the salt solution containing the manganese source, and therefore, the precipitant is used in an amount that at least ensures complete precipitation of manganese ions, although the precipitant may be used in an appropriate excess amount. After precipitation, the obtained manganese-containing precursor may be any one of manganese carbonate, manganese hydroxide, and the like. The manganese-containing precursor is formed into spheres or spheroids through precipitation reaction, namely, a regular sphere structure or an irregular sphere structure.
In step S02, the M-containing compound is selected from at least one of an oxide of M, a hydroxide of M, and a carbonate of M. Such as at least one of lithium oxide, lithium hydroxide, lithium carbonate, copper oxide, copper hydroxide, copper carbonate, tin dioxide, tin hydroxide, stannous carbonate, yttrium oxide, yttrium hydroxide, yttrium carbonate, niobium oxide, niobium hydroxide, niobium carbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, nickel oxide, nickel hydroxide, nickel carbonate, iron oxide, iron hydroxide, iron carbonate, zinc oxide, zinc hydroxide, zinc carbonate, titanium oxide, titanium hydroxide, cobalt oxide, cobalt hydroxide, cobalt carbonate, aluminum oxide, aluminum hydroxide, aluminum carbonate, and the like.
In some embodiments, the first heat treatment comprises a microwave radiation treatment or a resistive heating treatment. Wherein the microwave radiation treatment condition is constant temperature sintering for 10 min-1 h at 300-600 ℃; the condition of the resistance heating treatment is constant temperature sintering for 1-5 h at 300-600 ℃.
In step S03, a sodium-containing compound is involved selected from at least one of sodium carbonate or sodium hydroxide. The compound containing A is selected from carbonate of A or hydroxide of A, such as at least one of potassium carbonate, potassium hydroxide, magnesium carbonate, magnesium hydroxide, calcium carbonate, calcium hydroxide and aluminum carbonate.
In some embodiments, the second heat treatment comprises a microwave radiation treatment or a combination of a microwave radiation treatment and a resistive heating treatment. Wherein the microwave radiation treatment condition is that the constant temperature sintering is carried out for 10min to 1h at the temperature of 300 to 600 ℃, and then the constant temperature sintering is carried out for 1 to 3h at the temperature of 700 to 1000 ℃; the combination of microwave radiation and resistance heating is that resistance heating is adopted to sinter for 1-5 hours at a constant temperature of 300-600 ℃, then microwave radiation is adopted to heat up to 700-1000 ℃ and sinter for 1-3 hours at a constant temperature.
The preparation method has the characteristics of low-cost and easily-obtained raw materials, simple preparation process, high yield, low energy consumption and the like, and the obtained positive electrode material of the sodium ion battery has uniform appearance.
Based on the positive electrode material of the sodium ion battery, the third aspect of the invention also provides a sodium ion battery.
Specifically, the sodium ion battery comprises a positive plate, a negative plate and a diaphragm for isolating the positive plate and the negative plate. The positive plate comprises a positive electrode active layer, and the positive electrode active layer comprises the sodium ion battery positive electrode material.
The positive plate also contains a conductive agent and a binder.
In some embodiments, the positive plate is prepared by mixing the positive material of the sodium ion battery provided by the embodiment of the invention with a conductive agent, a binder and a solvent to prepare positive slurry, coating the positive slurry on the surface of a positive current collector such as aluminum foil, and drying, rolling and cutting the positive slurry to prepare the positive plate.
In some embodiments, the mass ratio of the sodium ion battery positive electrode material, the conductive agent and the binder in the positive electrode sheet is 70:20:10 or 80:10:10 or 90:5:5. In preparing the positive electrode slurry, the solvent may be N-methylpyrrolidone (NMP), and the solvent may also be deionized water or ethanol.
The sodium ion battery provided by the embodiment of the invention uses the anode active material of hard carbon, sodium metal, soft carbon or titanium-containing oxide.
The electrolyte of the sodium ion battery provided by the embodiment of the invention is 1MNAPF 6 Electrolyte solution/(EC: dmc=1:1), 1MNaPF 6 Electrolyte of PC, 1MNaClO 4 Any one of the electrolytes/(EC: pc=1:1). Wherein EC: dmc=1:1 represents ethylene carbonate and ethylmethyl carbonate according toSolvent formed in a volume ratio of 1:1, PC representing propylene carbonate, EC: PC represents a solvent formed by ethylene carbonate and propylene carbonate in a volume ratio of 1:1.
The separator used in the sodium ion battery provided by the embodiment of the invention is a polyolefin microporous membrane such as polyethylene, polypropylene and the like, such as Celgard separator.
In order to more effectively illustrate the technical solution of the present invention, the following description is made by means of a plurality of specific embodiments.
Example 1
A preparation method of a positive electrode material of a sodium ion battery comprises the following steps:
(a) Dissolving manganese sulfate in water to prepare 2mol/L manganese ion solution; and (3) dropwise adding 2mol/L sodium bicarbonate water solution serving as a precipitator into the manganese ion solution until manganese ions are completely precipitated, so as to obtain a manganese carbonate precursor.
(b) Mixing manganese carbonate and copper carbonate according to the stoichiometric ratio of the final product (the molar ratio of manganese to copper is 9:1), and then adopting microwave radiation to sinter at the constant temperature of 400 ℃ for 30min to obtain the oxide precursor.
(c) Mixing sodium carbonate, potassium carbonate and the oxide precursor according to the stoichiometric ratio of the final product (the molar ratio of sodium, potassium, manganese and copper is 19:1:18:2), then adopting a microwave radiation mode to perform constant-temperature sintering at 500 ℃ for 30min, then heating to 850 ℃ to perform constant-temperature sintering for 2h, and naturally cooling to room temperature to obtain a sample 1.
XRD test was performed on sample 1 obtained in example 1, and the specific test results are shown in FIG. 1.
As can be seen from the XRD pattern of FIG. 1, sample 1 obtained has a chemical composition of (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 And (Na) 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 With O 3 The standard XRD spectra of the phases are consistent, and the obtained material has a crystal structure of O 3 The phase can thus be determined for the as-prepared (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 Is O 3 And (3) phase crystals.
The obtained sample 1 was further subjected to a Scanning Electron Microscope (SEM) test, and the result is shown in fig. 2.
From fig. 2, it can be determined that sample 1 is formed from (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 The nano particles are assembled, the morphology of the nano particles is partially hollow sphere and partially hollow spheroid, and the wall body is provided with a porous structure, so that the positive electrode material of the sodium ion battery is determined to be formed by (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 The nano particles are assembled, and adjacent sodium ion battery anode materials are mutually piled, and the average diameter of each sodium ion battery anode material is between 1 and 10 mu m.
Example 2
A preparation method of a positive electrode material of a sodium ion battery comprises the following steps:
(a) And (3) dropwise adding 1mol/L sodium bicarbonate aqueous solution serving as a precipitator into the manganese nitrate aqueous solution until manganese ions are completely precipitated, so as to obtain a manganese carbonate precursor.
(b) Mixing manganese carbonate, nickel hydroxide and cobaltosic oxide according to the stoichiometric ratio of the final product (the molar ratio of manganese to nickel to cobalt is 67:23:10), and then adopting resistive heating to 400 ℃ and sintering at constant temperature for 5 hours to obtain the oxide precursor.
(c) Mixing sodium hydroxide, magnesium hydroxide and the oxide precursor (the molar ratio of sodium, magnesium, manganese, nickel and cobalt is 90:10:67:23:10) according to the stoichiometric ratio of the final product, then adopting resistance heating to sinter at the constant temperature of 500 ℃ for 5 hours, finally adopting microwave radiation to sinter at the constant temperature of 750 ℃ for 1 hour, and naturally cooling to the room temperature to obtain a sample 2.
XRD test was performed on sample 2 obtained in example 2, and the specific test results are shown in FIG. 3.
As can be seen from the XRD pattern of FIG. 3, the chemical formula is (Na 0.9 Mg 0.1 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 The method comprises the steps of carrying out a first treatment on the surface of the And the crystal structure of sample 2 was identical to that of O 3 The standard XRD spectra of the phases are consistent, and the obtained material has a crystal structure of O 3 The phase can thus be determined for the (Na) prepared in example 2 0.9 Mg 0.1 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 Is O 3 And (3) phase crystals.
Example 3
A preparation method of a positive electrode material of a sodium ion battery comprises the following steps:
(a) Dissolving manganese chloride in water to prepare a manganese ion solution with the concentration of 1 mol/L; and (3) dropwise adding 1mol/L sodium carbonate aqueous solution serving as a precipitator into the manganese ion solution until manganese ions are completely precipitated, so as to obtain a manganese carbonate precursor.
(b) Mixing manganese carbonate, stannous oxide and ferrous oxalate according to the stoichiometric ratio of the final product (the molar ratio of manganese to tin to iron is 5:2:3), heating to 500 ℃ by adopting microwave radiation, and sintering at constant temperature for 1h to obtain an oxide precursor.
(c) Mixing sodium carbonate, potassium carbonate and the oxide precursor according to the stoichiometric ratio of the final product (the molar ratio of sodium, calcium, manganese, tin and iron is 17:3:10:2:6), then adopting a microwave radiation mode to perform constant-temperature sintering at 400 ℃ for 30min, then heating to 800 ℃ to perform constant-temperature sintering for 1h, and naturally cooling to room temperature to obtain a sample 3.
XRD test was performed on sample 3 obtained in example 3, and the specific test results are shown in FIG. 4.
As can be seen from the XRD pattern of FIG. 4, the chemical formula is (Na 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 The method comprises the steps of carrying out a first treatment on the surface of the And the crystal structure of sample 3 was identical to that of O 3 The standard XRD spectra of the phases are consistent, and the obtained material has a crystal structure of O 3 The phase can thus be determined for the (Na) prepared in example 3 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 Is O 3 And (3) phase crystals.
Example 4
A preparation method of a positive electrode material of a sodium ion battery comprises the following steps:
(a) Dissolving manganese sulfate in water to prepare a manganese ion solution with the concentration of 1 mol/L; and (3) dropwise adding 1mol/L sodium carbonate aqueous solution serving as a precipitator into the manganese ion solution until manganese ions are completely precipitated, so as to obtain a manganese carbonate precursor.
(b) Mixing manganese carbonate, stannous oxide and ferrous oxalate according to the stoichiometric ratio of the final product (the molar ratio of manganese to magnesium to niobium is 80:16:4), and then adopting microwave radiation to sinter at the constant temperature of 500 ℃ for 1h to obtain an oxide precursor.
(c) Mixing sodium carbonate, potassium carbonate and the oxide precursor according to the stoichiometric ratio of the final product (the molar ratio of sodium, potassium, manganese, tin and iron is 20:5:20:4:1), then adopting a microwave radiation mode to perform constant-temperature sintering at 400 ℃ for 30min, then heating to 700 ℃ to perform constant-temperature sintering for 1h, and naturally cooling to room temperature to obtain a sample 4.
XRD test of sample 4 obtained in example 4 revealed that sample 4 was obtained having the chemical formula (Na 0.8 K 0.2 )(Mn 0.8 Mg 0.16 Nb 0.04 )O 2 And is O 3 And (3) phase (C).
Example 5
A preparation method of a positive electrode material of a sodium ion battery comprises the following steps:
(a) Dissolving manganese sulfate in water to prepare a manganese ion solution with the concentration of 1 mol/L; and (3) dropwise adding a 1mol/L sodium hydroxide aqueous solution serving as a precipitator into the manganese ion solution until manganese ions are completely precipitated, so as to obtain a manganese hydroxide precursor.
(b) Mixing manganese hydroxide, titanium dioxide and yttrium oxide according to the stoichiometric ratio of the final product (the molar ratio of manganese, titanium and yttrium is 12:7:1), and then adopting resistance heating to sinter at the constant temperature of 550 ℃ for 3 hours to obtain an oxide precursor.
(c) Mixing sodium hydroxide, aluminum oxide and the oxide precursor (the molar ratio of sodium, aluminum, manganese, titanium and yttrium is 19:1:12:7:1) according to the stoichiometric ratio of the final product, then adopting resistance heating to sinter at a constant temperature of 550 ℃ for 3 hours, finally adopting microwave radiation to sinter at a constant temperature of 750 ℃ for 1 hour, and naturally cooling to room temperature to obtain a sample 5.
XRD test of sample 5 obtained in example 5 revealed that sample 5 was obtained having the chemical formula (Na 0.95 Al 0.05 )(Mn 0.6 Ti 0.35 Y 0.05 )O 2 And is O 3 And (3) phase (C).
Example 6
A preparation method of a positive electrode material of a sodium ion battery comprises the following steps:
(a) Dissolving manganese sulfate in water to prepare 2mol/L manganese ion solution; and (3) dropwise adding 2mol/L sodium bicarbonate water solution serving as a precipitator into the manganese ion solution until manganese ions are completely precipitated, so as to obtain a manganese carbonate precursor.
(b) Mixing manganese carbonate and copper carbonate according to the stoichiometric ratio of the final product (the molar ratio of manganese to copper is 9:1), and then adopting microwave radiation to sinter at the constant temperature of 400 ℃ for 30min to obtain the oxide precursor.
(c) Mixing sodium carbonate and the oxide precursor according to the stoichiometric ratio of the final product (the molar ratio of sodium, manganese and copper is 10:9:1), then adopting a microwave radiation mode to perform constant-temperature sintering at 500 ℃ for 30min, then heating to 850 ℃ to perform constant-temperature sintering for 2h, and naturally cooling to room temperature to obtain a sample 6.
XRD testing of sample 6 revealed that sample 6 had a chemical formula of Na (Mn 0.9 Cu 0.1 )O 2 And is O 3 And (3) phase (C).
Example 7
A preparation method of a positive electrode material of a sodium ion battery comprises the following steps:
(a) Dissolving manganese sulfate and copper sulfate in water according to a mol ratio of 9:1 to prepare a manganese ion solution with a concentration of 1 mol/L; and (3) dropwise adding a 1mol/L sodium hydroxide aqueous solution serving as a precipitator into the manganese ion solution until manganese ions are completely precipitated, so as to obtain a hydroxide precursor.
(b) Mixing sodium carbonate, potassium carbonate and hydroxide precursors (the molar ratio of sodium, potassium, manganese and copper is 19:1:18:2) according to the stoichiometric ratio of the final product, then adopting a resistance heating mode to perform constant-temperature sintering at 500 ℃ for 3 hours, then heating to 850 ℃ to perform constant-temperature sintering for 20 hours, and naturally cooling to room temperature to obtain a sample 7.
XRD testing of sample 7 revealed that sample 7 had a chemical formula (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 And is O 3 And (3) phase (C).
SEM testing was performed on the sample obtained in example 7, and the specific test results are shown in fig. 5.
As can be seen from fig. 5, the morphology of the material obtained in example 7 is irregular microparticles.
In order to demonstrate the performance of the materials obtained in the present invention, the materials prepared in examples 1 to 5 were used as positive electrode materials for sodium ion batteries, respectively, and assembled into sodium ion batteries, and the corresponding performance was tested.
Application example 1
A preparation method of the sodium ion battery comprises the following steps:
(1) The positive electrode material of the sodium ion battery obtained in the example 1 is used as a positive electrode active material, is mixed with conductive carbon black and polyvinylidene fluoride (PVdF) binder according to the mass ratio of 7:2:1, is dissolved in N-methyl pyrrolidone (NMP) solvent to prepare positive electrode slurry, is coated on aluminum foil, and is dried and cut to obtain a positive electrode plate.
(2) Assembling the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1MNAPF 6 The electrolyte formed by dissolving in the mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1) was left to stand for 24h after assembly.
Application example 2
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the sodium ion battery anode material obtained in the example 2 as an anode active material, mixing the anode active material with conductive carbon black and PVdF binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1MNAPF 6 The electrolyte formed by dissolving in the mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1) was left to stand for 24h after assembly.
Application example 3
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the sodium ion battery anode material obtained in the example 3 as an anode active material, mixing the anode active material with conductive carbon black and PVdF binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1MNAPF 6 The electrolyte formed by dissolving in the mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1) was left to stand for 24h after assembly.
Application example 4
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the sodium ion battery anode material obtained in the example 4 as an anode active material, mixing the anode active material with conductive carbon black and PVdF binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1MNAPF 6 The electrolyte formed by dissolving in the mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1) was left to stand for 24h after assembly.
Application example 5
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the sodium ion battery anode material obtained in the example 5 as an anode active material, mixing the anode active material with conductive carbon black and PVdF binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1MNAPF 6 Dissolved in EC (ethylene carbonate)And an electrolyte formed in a DMC (dimethyl carbonate) mixture (in volume ratio EC: dmc=1:1), and standing for 24 hours after assembly.
And (3) respectively performing charge and discharge activation tests after the sodium ion batteries assembled in the application examples 1 to 5 are qualified in voltage detection.
Specifically, the test includes:
(1) First charge-discharge specific capacity: three charges and discharges were performed at a current density of 20mA/g in the voltage range of 1.8-4.5V.
(2) And (3) testing the cycle performance: the cycle performance test was performed by charging at a current density of 40mA/g in a voltage range of 1.8-4.5V and sequentially discharging 100 cycles at a current density of 200 mA/g.
(3) And (3) multiplying power performance test: the charging was performed at a current density of 40mA/g in a voltage range of 1.8-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at a current density of 40mA/g, 100mA/g, 200mA/g, 500mA/g, and 1000 mA/g.
The test results are shown in Table 1.
Table 1 statistical results of electrochemical performance tests of application examples 1 to 5
As can be seen from Table 1, the specific capacity of the first-turn discharge in application example 1 was 231mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is up to 177mAh/g; at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 138mAh/g; the capacity retention was about 88% over 100 charge and discharge cycles at a current density of 200mA/g (about 1C).
The specific capacity of the first-turn discharge of application example 2 is 223mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), a specific discharge capacity of up to 153mAh/g; at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 105mAh/g; the capacity retention was about 85% over 100 charge and discharge cycles at a current density of 200mA/g (about 1C).
The first-turn discharge specific capacity of application example 3 is 215mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is up to 138mAh/g; at a current density of 1000mA/g (about 5C), the specific discharge capacity was 87mAh/g; the capacity retention was about 83% over 100 charge and discharge cycles at a current density of 200mA/g (about 1C).
The first-turn discharge specific capacity of application example 4 is 196mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is 121mAh/g; at a current density of 1000mA/g (about 5C), the specific discharge capacity was 82mAh/g; the capacity retention was about 90% over 100 charge and discharge cycles at a current density of 200mA/g (about 1C).
The first-turn discharge specific capacity of application example 5 is 182mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity was 83mAh/g; at a current density of 1000mA/g (about 5C), the specific discharge capacity was 53mAh/g; the capacity retention was about 91% over 100 charge and discharge cycles at a current density of 200mA/g (about 1C).
The positive electrode materials of the sodium ion batteries obtained in examples 1 to 5 were assembled into sodium ion full batteries respectively, and the sodium ion full batteries of application examples 6 to 10 were obtained correspondingly, and the preparation methods thereof were referred to the preparation method of application example 1, except that the hard carbon was used as the negative electrode in application examples 6 to 10 instead of sodium metal, and the preparation method of the full battery was not discussed again for the sake of economy.
Referring to the test methods of application examples 1 to 5, electrochemical performance tests were performed on the full cells of application examples 6 to 10, and the results are shown in table 2.
Table 2 statistical results of full cell electrochemical performance tests of application examples 6 to 10
As can be seen from Table 2, the specific capacity of the initial charge/discharge of the full cell of application example 6 and the hard carbon loading was 197mAh/g (charge/discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is up to 151mAh/g; at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 112mAh/g; the capacity retention was about 92% over 500 charge and discharge cycles at a current density of 200mA/g (about 1C).
Application example 7 and hard carbon loaded full battery have a first-cycle discharge specific capacity of 198mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is as high as 134mAh/g; at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 94mAh/g; the capacity retention was about 91% over 500 charge and discharge cycles at a current density of 200mA/g (about 1C).
Application example 8 and hard carbon loaded full battery have a first-cycle discharge specific capacity of 196mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is up to 112mAh/g; at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 70mAh/g; the capacity retention was about 91% over 500 charge and discharge cycles at a current density of 200mA/g (about 1C).
Application example 9 and hard carbon loaded full battery have a first-cycle discharge specific capacity of 183mAh/g (charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is up to 101mAh/g; at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 67mAh/g; the capacity retention was about 93% over 500 charge and discharge cycles at a current density of 200mA/g (about 1C).
The specific capacity of the initial ring discharge of the full battery loaded by application example 10 and hard carbon is 173mAh/g (the charge-discharge current density of 20mA/g, about 0.1C); at a current density of 200mA/g (about 1C), the specific discharge capacity is up to 65mAh/g; at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 40mAh/g; the capacity retention was about 94% over 500 charge and discharge cycles at a current density of 200mA/g (about 1C).
Comparative example 1
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the sodium ion battery anode material obtained in the example 6 as an anode active material, mixing the anode active material with conductive carbon black and PVdF binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1MNAPF 6 The electrolyte formed by dissolving in the mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1) was left to stand for 24h after assembly.
Comparative example 2
A preparation method of the sodium ion battery comprises the following steps:
(1) And taking the sodium ion battery anode material obtained in the example 7 as an anode active material, mixing the anode active material with conductive carbon black and PVdF binder according to the mass ratio of 7:2:1, dissolving the mixture in N-methyl pyrrolidone (NMP) solvent to prepare anode slurry, coating the anode slurry on aluminum foil, drying and cutting to obtain the anode plate.
(2) Assembling the positive plate obtained in the step (1) with sodium metal and Celgard diaphragm to form a sodium ion battery, wherein the electrolyte of the sodium ion battery is 1MNAPF 6 The electrolyte formed by dissolving in the mixture of EC (ethylene carbonate) and DMC (dimethyl carbonate) (in volume ratio EC: dmc=1:1) was left to stand for 24h after assembly.
Electrochemical performance tests were performed on comparative examples 1 and 2.
Specifically, the test includes:
(1) First charge-discharge specific capacity: three charges and discharges were performed at a current density of 20mA/g in the voltage range of 1.8-4.5V.
(2) And (3) testing the cycle performance: the cycle performance test was performed by charging at a current density of 40mA/g in a voltage range of 1.8-4.5V and sequentially discharging 100 cycles at a current density of 200 mA/g.
(3) And (3) multiplying power performance test: the charging was performed at a current density of 40mA/g in a voltage range of 1.8-4.5V, and the rate performance test was performed by sequentially discharging 5 cycles at a current density of 40mA/g, 100mA/g, 200mA/g, 500mA/g, and 1000 mA/g.
The test results are shown in fig. 6, 7 and 8.
As can be seen from fig. 6, when the sodium ion batteries obtained in application example 1, comparative example 1 and comparative example 2 were charged to 4.5V, the characteristic absorption peak of the peroxo ion appears in application example 1 at 523.5eV, the characteristic absorption peak of the peroxo ion appears in comparative example 2 at 524eV, and the characteristic absorption peak of the peroxo ion does not appear in the corresponding position in comparative example 1, which means that doping of potassium (K) in the materials of application example 1 and comparative example 2 activates the activity of O anion, so that O participates in the redox reaction to contribute to capacity, while the O anion does not have activity without doping of K. From this, it was found that the materials obtained in example 1 and example 7 were able to activate the anionic activity to increase the specific capacity and the structural stability was able to be improved, whereas the material of example 6 was unable to activate the anionic activity and the specific capacity and structural stability of the material were unable to be improved. As can be seen from the data of table 1 in fig. 6, the specific capacities of application examples 2 to 5 are also improved to different degrees, so that it can be inferred that doping of element a activates the activity of O anions, so that O participates in the redox reaction to contribute to capacity, and the specific capacity of the positive electrode material of the sodium ion battery obtained in the embodiment of the invention is higher than that of the conventional layered sodium transition oxide.
From the cycle performance curve shown in FIG. 7, it can be seen that the capacity retention rate was about 88% by 100 charge and discharge cycles at a current density of 200mA/g (about 1C) in application example 1; while comparative example 1 had a capacity retention of about 73% over 100 charge and discharge cycles at a current density of 200mA/g (about 1C). In addition, application example 1 had a higher initial discharge specific capacity during cycling.
Referring to fig. 8, table 1 and table 2, it can be seen that application example 1 has a specific discharge capacity of up to 177mAh/g at a current density of 200mA/g (about 1C), a specific discharge capacity of up to 138mAh/g at a current density of 1000mA/g (about 5C), a specific discharge capacity of up to 151mAh/g at a current density of 200mA/g (about 1C) and a specific discharge capacity of up to 112mAh/g at a current density of 1000mA/g (about 5C); whereas comparative example 2, which has a specific discharge capacity of 129mAh/g at a current density of 200mA/g (about 1C); at a current density of 1000mA/g (about 5C), the specific discharge capacity was almost attenuated to zero, and the specific discharge capacities at the corresponding current densities of application example 2 to application example 5 were also significantly higher than that of the irregular microparticles obtained in comparative example 2, i.e., the rate capability of the hollow microsphere particles was superior to that of the solid irregular microparticles. The full batteries of application examples 7 to 10 also release higher specific capacity, rate capability, and have better capacity retention. Therefore, compared with the prior art, the sodium ion battery anode material provided by the embodiment of the invention can effectively improve the multiplying power discharging capacity.
The foregoing description of the preferred embodiment of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The positive electrode material of the sodium ion battery is characterized in that the shape of the positive electrode material of the sodium ion battery is a hollow sphere and/or spheroid; the wall body of the positive electrode material of the sodium ion battery is provided with a porous structure;
the positive electrode material of the sodium ion battery is formed by self-assembly of nano particles;
the nano particles are layered sodium transition metal oxides.
2. The sodium ion battery positive electrode material of claim 1, further comprising at least one of the following technical features:
(1) The average diameter of the positive electrode material of the sodium ion battery is 1-10 mu m;
(2) The average particle diameter of the nano particles is 60 nm-200 nm;
(3) The layered sodium transition metal oxide has the general formula:
(Na 1-x A x )(Mn 1-y M y )O 2 ；
wherein A is at least one selected from K, mg, ca, al;
m is selected from at least one of Li, cu, sn, Y, nb, mg, ni, fe, zn, ti, co, al;
0<x≤0.2；0≤y≤0.5；
(4) The porous structure is formed by mutually stacking and enclosing adjacent nano particles in the same positive electrode material particles of the sodium ion battery;
(5) The crystal structure of the layered sodium transition metal oxide is O3 phase.
3. A sodium ion battery positive electrode material according to claim 1, wherein the nanoparticles comprise (Na 0.95 K 0.05 )(Mn 0.9 Cu 0.1 )O 2 Nanoparticles, (Na) 0.90 Mg 0.10 )(Mn 0.67 Ni 0.23 Co 0.1 )O 2 Nanoparticles, (Na) 0.85 Ca 0.15 )(Mn 0.5 Sn 0.2 Fe 0.3 )O 2 Nanoparticles, (Na) 0.8 K 0.2 )(Mn 0.8 Mg 0.16 Nb 0.04 )O 2 Nanoparticles, (Na) 0.95 Al 0.05 )(Mn 0.6 Ti 0.35 Y 0.05 )O 2 At least one of the nanoparticles.
4. A method for preparing a positive electrode material for sodium ion battery according to any one of claims 1 to 3, comprising the steps of:
mixing a salt solution containing a manganese source with a precipitant, and precipitating by adopting a precipitation method to obtain a manganese-containing precursor;
mixing an M-containing compound with the manganese-containing precursor according to the stoichiometric ratio of the final product, and performing first heat treatment to obtain an oxide precursor;
mixing a sodium-containing compound, an A-containing compound and the oxide precursor according to the stoichiometric ratio of the final product, and performing second heat treatment to obtain the final product;
wherein M is selected from at least one of Li, cu, sn, Y, nb, mg, ni, fe, zn, ti, co, al;
a is selected from at least one of K, mg, ca, al.
5. The method for producing a positive electrode material for a sodium ion battery according to claim 4, wherein the salt solution is at least one selected from the group consisting of manganese-containing sulfate and hydrate thereof, manganese-containing nitrate and hydrate thereof, manganese-containing chloride and hydrate thereof.
6. The method for preparing a positive electrode material for sodium ion battery according to claim 3, wherein the precipitant is at least one selected from the group consisting of sodium hydroxide, sodium carbonate and sodium bicarbonate; the usage amount of the precipitant at least ensures that manganese in the salt solution is completely precipitated;
the M-containing compound is at least one selected from the group consisting of an oxide of M, a hydroxide of M and a carbonate of M.
7. The method for producing a sodium ion battery positive electrode material according to any one of claims 4 to 6, wherein the first heat treatment is selected from microwave radiation or resistance heating;
the microwave radiation condition is that sintering is carried out for 10min to 1h at the constant temperature of 300 to 600 ℃;
the resistance heating condition is that sintering is carried out for 1h to 5h at the constant temperature of 300 ℃ to 600 ℃.
8. The method for producing a sodium ion battery positive electrode material according to any one of claims 4 to 6, wherein the sodium-containing compound is at least one selected from sodium carbonate and sodium hydroxide;
the compound containing A is at least one selected from carbonate containing A and hydroxide containing A.
9. The method for preparing a positive electrode material for a sodium ion battery according to any one of claims 4 to 6, wherein the second heat treatment is selected from microwave radiation or a combination of microwave radiation and resistance heating;
The microwave radiation condition is that the constant temperature sintering is carried out for 10min to 1h at 300 to 600 ℃, and then the constant temperature sintering is carried out for 1 to 3h at 700 to 1000 ℃;
the combination of microwave radiation and resistance heating is that resistance heating is adopted to sinter for 1-5 hours at a constant temperature of 300-600 ℃, then microwave radiation is adopted to heat up to 700-1000 ℃ and sinter for 1-3 hours at a constant temperature.
10. A sodium ion battery comprising a positive electrode active layer, wherein the positive electrode active layer comprises the sodium ion battery positive electrode material according to any one of claims 1 to 3, or comprises the sodium ion battery positive electrode material prepared by the preparation method of the sodium ion battery positive electrode material according to any one of claims 4 to 9.
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