CN114530590A - High-entropy oxide negative electrode energy storage material containing bismuth, tin and antimony and preparation method and application thereof - Google Patents
High-entropy oxide negative electrode energy storage material containing bismuth, tin and antimony and preparation method and application thereof Download PDFInfo
- Publication number
- CN114530590A CN114530590A CN202210099616.3A CN202210099616A CN114530590A CN 114530590 A CN114530590 A CN 114530590A CN 202210099616 A CN202210099616 A CN 202210099616A CN 114530590 A CN114530590 A CN 114530590A
- Authority
- CN
- China
- Prior art keywords
- antimony
- tin
- entropy oxide
- bismuth
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000004146 energy storage Methods 0.000 title claims abstract description 29
- 239000011232 storage material Substances 0.000 title claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 24
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052718 tin Inorganic materials 0.000 title claims abstract description 24
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 23
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000000137 annealing Methods 0.000 claims abstract description 36
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 24
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- 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 14
- 239000011734 sodium Substances 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 4
- 239000011777 magnesium Substances 0.000 claims abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 4
- 239000011733 molybdenum Substances 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000011701 zinc Substances 0.000 claims abstract description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- LESWRIKTQXPFLL-UHFFFAOYSA-N [Sb].[Sn].[Bi] Chemical compound [Sb].[Sn].[Bi] LESWRIKTQXPFLL-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000004729 solvothermal method Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- 238000003980 solgel method Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000006641 stabilisation Effects 0.000 abstract description 7
- 238000011105 stabilization Methods 0.000 abstract description 7
- 238000007599 discharging Methods 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000005204 segregation Methods 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- -1 bismuth-tin-antimony-cobalt-indium Chemical compound 0.000 description 23
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 19
- 239000000843 powder Substances 0.000 description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical group 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 238000010345 tape casting Methods 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910019398 NaPF6 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BMYPOELGNTXHPU-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxastibolan-2-yl) oxalate Chemical compound [Sb+3].[Sb+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BMYPOELGNTXHPU-UHFFFAOYSA-H 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 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
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 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
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 239000011787 zinc oxide Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a high-entropy oxide cathode energy storage material containing bismuth, tin and antimony, and a preparation method and application thereof, wherein the material is a five-element or above multi-element high-entropy oxide material consisting of one or more elements of bismuth, tin and antimony and nickel, cobalt, manganese, copper, chromium, iron, indium, germanium, magnesium, aluminum, zinc, molybdenum, tungsten, vanadium or titanium; preparing a uniform composite precursor from the element metal salt by one of physical ball milling, freeze drying, solvothermal, sol-gel or coprecipitation methods; and then placing the obtained precursor in an annealing furnace, and annealing for 0.5-48 hours at 300-700 ℃ in the air. The entropy stabilization effect and the phase stabilization effect are used as negative electrode materials of potassium, sodium and lithium ion batteries, so that the internal stress generated by the volume change of metal oxide negative electrode particles in the charging and discharging processes is relieved, the expansion of cracks in the particles is inhibited, the pulverization and component segregation of the negative electrode particles are avoided, the integrity of the electrode is maintained, and the structure is stable and the cycle performance is good.
Description
Technical Field
The invention belongs to the technical field of potassium, sodium and lithium ion batteries, and particularly relates to a bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material as well as a preparation method and application thereof.
Background
Lithium Ion Batteries (LIBs) that are currently commercialized have difficulty meeting the requirement of large-scale energy storage due to the limited storage capacity and price of lithium resources. Compared with lithium, sodium and potassium have abundant natural resources and low price, and have a working mechanism similar to that of a lithium ion battery. Therefore, sodium and potassium ion batteries may be used as a substitute for lithium ion batteries. At present, researches on lithium, sodium and potassium ion battery cathode materials mainly focus on carbon-based materials with low specific capacity, have the characteristics of good conductivity, rich structure, low price and the like, are widely applied to secondary ion battery cathode materials, and have the problems of low specific capacity and low stacking density.
Transition Metal Oxide (TMO) is considered as an electrode material for a next-generation secondary ion battery because of its higher theoretical capacity. Compared with the graphite cathode, the working voltage of the TMO is relatively high, and the conversion reaction mechanism realizes the multi-electron oxidation-reduction reaction in the charging and discharging processes, so that the TMO cathode shows larger theoretical specific capacity and higher safety compared with the graphite cathode. However, the conventional TMO cathode will generally undergo a complex phase transition process and a large volume change during charge and discharge, and the serious structural change caused thereby immediately causes a main reason for the rapid capacity decay of the TMO cathode.
The high-entropy oxide has good ion storage performance due to its entropy stabilization effect, and is considered to be a promising negative electrode material in an ion battery. The complex elements in the high entropy oxides used in the negative electrode materials may cause a gradual redox reaction, not just a one electron exchange, providing a larger theoretical specific capacity. Furthermore, the high entropy oxide can operate at a relatively high voltage compared to the graphite anode, which may be beneficial in terms of safety.
The lattice of the high entropy oxide is considered to be severely distorted due to the presence of atoms of different sizes in the oxide. The serious lattice distortion is one of the reasons that the diffusion dynamics in the high-entropy oxide is slow and the strength is high, the internal stress generated by the volume change of the metal oxide negative electrode particles in the charging and discharging process can be effectively relieved, the expansion of cracks in the particles is inhibited, the pulverization and the component segregation of the negative electrode particles are avoided, and the integrity of the electrode is maintained, so that the characteristics of stable structure, good cycle performance and the like are obtained. At present, the high-entropy oxide negative electrode is mainly applied to a lithium ion battery, and the application and research of the high-entropy oxide negative electrode in the aspect of a potassium ion battery are in a blank stage. The introduction of the high-entropy concept into the potassium ion battery is believed to be helpful for overcoming the problem of severe volume change in the charging and discharging processes of the metal oxide negative electrode material, and has important significance for developing the high-energy-density potassium ion battery.
At present, transition metal bismuth and a nano-structure compound thereof show excellent potassium storage performance in ether electrolyte, but the theoretical capacity is low. The actual potassium storage capacity of the transition metal tin is lower, while the transition metal antimony has higher theoretical capacity, but the deterioration degree of the cycling stability caused by volume change is obviously higher than that of bismuth-based and tin-based negative electrodes. In addition, although the relative reserves of the three transition metal elements in China are high, the total reserves are not large, so that the influence of stress generated by the volume change of the transition metal on the integrity of the material is expected to be inhibited by introducing high entropy through developing the multi-element composite high-entropy oxide negative electrode material, and potential related problems caused by single resource shortage can be avoided.
The prior published patent CN 110190259A for taking a high-entropy oxide material as an ion battery cathode discloses a preparation method of a nano high-entropy oxide and a lithium ion battery cathode material, wherein iron oxide, titanium oxide, magnesium oxide, zinc oxide and copper oxide powder are mixed according to the stoichiometric ratio of equimolar metal atoms, and the mixture is subjected to ball milling, cold briquetting, high-temperature sintering and ball milling again to obtain the high-entropy oxide (FeTiMgZnCu)3O4(ii) a And then according to the mass percent of each component: (FeTiMgZnCu)3O4Preparing a lithium ion battery cathode electrode plate by using 70% of nano powder, 20% of acetylene black and 10% of binder; one-step synthesis of high-entropy oxide (FeTiMgZnCu) by high-temperature solid-phase method3O4The block material is obtained by high-energy ball millingTo nano (FeTiMgZnCu) in a lamellar structure3O4The powder has simple operation process, low cost and no pollution; using said high entropy oxide (FeTiMgZnCu)3O4The prepared lithium ion battery negative electrode material can keep higher specific capacity under the charge-discharge current density of 100mA/g and has excellent cycling stability.
The prior published patent CN 108933248A for taking a high-entropy oxide material as an ion battery cathode discloses a preparation method of a spinel-type spherical high-entropy oxide material as a lithium ion battery cathode material, belonging to the field of lithium ion battery cathode materials. The method combines a chemical reduction method and low-temperature heat treatment, and specifically comprises the following steps: chloride, sulfate, nitrate, carbonate, acetate and oxalate of cobalt, chromium, copper, iron and nickel are used as metal sources, sodium borohydride and sodium hydrosulfite are used as reducing agents, and then products of redox reaction are calcined in equipment at 300-500 ℃ to obtain target products. The preparation method adopts liquid-phase ingredients, ensures that the raw materials are uniformly mixed at the molecular level, and realizes the stoichiometric ratio of the product; meanwhile, the method has the characteristics of simple process, mild reaction, short time, high efficiency, no special requirement on calcining equipment and the like, and the prepared high-entropy oxide powder has high purity, small granularity, higher initial discharge capacity and better cycle performance.
Compared with the existing published patents about high-entropy oxides, the preparation process of the material is various, the preparation process is simple, industrialization can be realized, the application range of the material is wider, the material can be applied to lithium ion battery cathode materials, excellent performances are shown in potassium ion batteries and sodium ion batteries, the shortage in the field of the cathode materials of the sodium ion batteries and the potassium ion batteries in this respect is made up, and the technical problems of low capacity, rapid capacity attenuation, unstable cycle performance and the like of the cathode materials of the lithium ion batteries, the sodium ion batteries and the potassium ion batteries are solved.
Disclosure of Invention
The technical problem to be solved is as follows: in order to overcome the defects in the prior art, the application provides a bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material, and a preparation method and application thereof, so as to solve the technical problems of low capacity, poor conductivity, unstable cycle performance and the like of the conventional lithium, sodium and potassium ion battery negative electrode material in the prior art.
The technical scheme is as follows:
the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony takes two or more metal salts of nickel, cobalt, manganese, copper, chromium, iron, indium, germanium, magnesium, aluminum, zinc, molybdenum, tungsten, vanadium and titanium and one or more metal salts of bismuth, tin and antimony as raw materials to form five-membered and above multi-element high-entropy oxide; wherein the proportion of each metal element is 5-35%, the sum of the atomic proportions of all the metal elements is 1, five-element or above multi-element high-entropy oxide precursors are synthesized by one of the methods of physical ball milling, freeze drying, solvent heating, sol-gel or coprecipitation, and then the target product is obtained by annealing under the air.
The preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: preparing a high-entropy oxide precursor by using five or more than five metal salts as raw materials by one of methods of physical ball milling, freeze drying, solvent heating, sol-gel or coprecipitation;
the second step is that: and (3) placing the high-entropy oxide precursor in an annealing furnace to carry out annealing treatment in the air, and grinding the material after the annealing is finished to obtain the high-entropy oxide material.
As a preferred technical scheme of the application: the physical ball milling method in the first step is that the ball milling rotating speed is 400--1The ball milling time is 5-15 h.
As a preferred technical scheme of the application: in the first step, the freeze drying method comprises the steps of adding metal salt into a centrifuge tube, adding 30mL of ultrapure water, putting into liquid nitrogen for freezing for 0.5h, and then putting into a freeze dryer for drying for 48 h.
As a preferred technical scheme of the application: the solvothermal method in the first step is to prepare a mixed solution of tetrabutyl titanate and ethylene glycol, add metal salt, stir, perform solvothermal reaction at the temperature of 100-200 ℃, the reaction time is 10-20h, and perform suction filtration, cleaning, drying and grinding after the reaction is finished.
As a preferred technical scheme of the application: in the first step, the sol-gel method is to add metal salt and citric acid with the molar mass of two parts of metal salt into 60ml of ethylene glycol solution, stir for 3 hours, and then carry out solvothermal reaction at the temperature of 130-150 ℃, wherein the reaction time is 6 hours.
As a preferred technical scheme of the application: the coprecipitation method in the first step is to dissolve metal salt in 50ml of ultrapure water, add two parts of sodium carbonate with the molar mass of the metal salt, and rotate at the rotating speed of 1000r min-1Stirring for 8h, carrying out suction filtration after the reaction is finished, and cleaning, drying and grinding a filter cake by using ethanol.
As a preferred technical scheme of the application: the metal salt in the first step comprises an acetate, a nitrate, a chloride, a carbonate, an oxalate or a sulfate.
As a preferred technical scheme of the application: in the second step, the annealing temperature is 300-700 ℃, and the annealing time is 0.5-48 h.
The application also discloses application of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony in cathode materials of lithium, sodium and potassium ion batteries.
As a preferred technical scheme of the application: the lithium ion battery assembling process is that high-entropy oxide, acetylene black and PVDF (polyvinylidene fluoride) are mixed according to the mass ratio of 8: 1:1 in NMP (N-methyl pyrrolidone) for 6 hours; uniformly coating the mixture on a copper foil by using a scraper through a tape casting method; the operation of installing the button cell is carried out in an argon atmosphere glove box, the counter electrode is a lithium sheet, the diaphragm is made of PP material, and the electrolyte is 1mol LiPF6in EC DMC: EMC ═ 1:1: 1).
As a preferred technical scheme of the application: the sodium ion battery assembly process comprises the steps of preparing high-entropy oxide, acetylene black and PVDF (polyvinylidene fluoride)Ethylene) in a mass ratio of 8: 1:1 in NMP (N-methyl pyrrolidone) for 6 hours; uniformly coating the mixture on a copper foil by using a scraper through a tape casting method; the operation of installing the button cell is carried out in an argon atmosphere glove box, the counter electrode is a sodium sheet, the diaphragm is made of glass fiber, and the electrolyte is 2mol NaPF6in DIGLYME solution.
As a preferred technical scheme of the application: the potassium ion battery assembling process is that high-entropy oxide, acetylene black and PVDF (polyvinylidene fluoride) are mixed according to the mass ratio of 8: 1:1 in NMP (N-methyl pyrrolidone) for 6 hours; uniformly coating the mixture on a copper foil by using a scraper through a tape casting method; and (3) carrying out button cell assembly operation in an argon atmosphere glove box, wherein the counter electrode is a potassium sheet, the diaphragm is made of glass fiber, and the electrolyte is 5mol of KFSI in DIGLYME solution.
Principle explanation: five or more than five metal salts are used as reaction raw materials and a multi-metal source, the metal salts are uniformly mixed by a physical ball milling method, a freeze drying method, a solvent heating method, a sol-gel method or a coprecipitation method, and then annealing treatment is carried out on the mixture in the air to obtain the corresponding high-entropy oxide.
Has the advantages that:
1. compared with the prior published patents on the high-entropy oxide material as the cathode of the ion battery, the high-entropy oxide material has relatively high specific capacity and excellent cycling stability due to the entropy stabilizing effect and the phase stabilizing effect.
2. The bismuth-tin-antimony-containing high-entropy oxide has good conductivity and high specific capacity.
3. The entropy stabilization effect and the phase stabilization effect can effectively inhibit the aggregation and crack propagation of particles in the charging and discharging processes of the high-entropy oxide cathode, the integrity of the electrode is ensured, and the high-entropy oxide cathode has good cycle performance and stable structure.
4. The method has the advantages of simple preparation method, short period, easily obtained raw materials, low cost and great industrial application value.
5. The material of the invention has wider application field, is not only limited to the cathode material of the lithium ion battery, but also can be applied to the sodium and potassium ion batteries, and has better application prospect in a plurality of fields such as catalytic reaction, optical material and the like.
6. The material benefits from entropy stabilization effect and phase stabilization effect, and can be used as a negative electrode material of a potassium/sodium/lithium ion battery, so that the internal stress generated by the volume change of metal oxide negative electrode particles in the charging and discharging processes can be effectively relieved, the expansion of cracks in the particles is inhibited, the pulverization and component segregation of the negative electrode particles are avoided, and the integrity of the electrode is maintained, so that the characteristics of stable structure, good cycle performance and the like are obtained.
7. The bismuth-tin-antimony-cobalt-indium five-membered high-entropy oxide prepared by a dry ball milling method is used as a negative electrode material of a lithium ion battery and is added into 0.5Ag-1The specific discharge capacity of the first circle is 1658mAh g under the high current density-1The charging specific capacity is 1108mAh g-1After 80 cycles of circulation, 378mAh g is kept-1Higher specific capacity.
8. The bismuth-tin-antimony-cobalt-indium five-element high-entropy oxide prepared by a dry ball milling method is used as a negative electrode material of a sodium ion battery and is added into 0.1Ag-1Under the current density of the high-capacity lithium ion battery, the coulombic efficiency of the first circle is up to 80 percent, and the specific discharge capacity of the first circle is 677mAh g-1The charging specific capacity is 545mAh g-1The capacity decayed slowly, after circulating 50 circles, 361mAh g still exists-1The specific capacity of (A).
9. The bismuth-tin-antimony-cobalt-indium five-element high-entropy oxide prepared by a dry ball milling method is used as a potassium ion battery cathode material and is coated on 0.1Ag-1The initial specific discharge capacity is 604mAh g at the current density of-1And the charging specific capacity is 338mAh g-1The coulombic efficiency of the first circle is 56 percent, and the charging specific capacity after 100 circles of circulation is 334mAh g-1And the high specific capacity and the excellent cycling stability are shown.
Drawings
FIG. 1 is an XRD pattern of a high entropy oxide material produced by ball milling in accordance with the present application.
FIG. 2 is an SEM image of a high entropy oxide material made by ball milling in accordance with the present application.
FIG. 3 is a charge-discharge curve diagram of the high-entropy oxide material prepared by ball milling in the application as the negative electrode of the lithium ion battery.
FIG. 4 is a long cycle performance graph of a high-entropy oxide material prepared by ball milling according to the present application as a negative electrode of a lithium ion battery.
FIG. 5 is a charge-discharge curve diagram of the high-entropy oxide material prepared by ball milling in the application as the negative electrode of the sodium-ion battery.
FIG. 6 is a graph of the long cycle performance of the high-entropy oxide material prepared by ball milling in the application as the negative electrode of the sodium-ion battery.
FIG. 7 is a charge-discharge curve diagram of the high-entropy oxide material prepared by ball milling in the application as the negative electrode of the potassium ion battery.
FIG. 8 is a graph of the long cycle performance of the high-entropy oxide material prepared by ball milling in the application as a negative electrode of a potassium ion battery.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and specific examples, which are only used for illustrating the present invention and are not limited to the following examples. It is intended to cover by the present invention all such modifications as come within the scope of the invention as defined by the appended claims.
In the following examples, one or more of three elements of bismuth, tin and antimony and metal salts of nickel, cobalt, manganese, copper, chromium, iron, indium, germanium, magnesium, aluminum, zinc, molybdenum, tungsten, vanadium or titanium are used as metal ion sources, five-element or higher high-entropy oxide precursors are prepared by physical ball milling, freeze drying, solvothermal, sol-gel or coprecipitation methods, then bismuth-tin-antimony-containing high-entropy oxides are generated by annealing in air, and lithium, sodium and potassium ion battery cathodes are manufactured by using the materials, and relevant tests are performed.
Example 1:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: weighing equal molar amounts of cobalt carbonate, indium acetate, bismuth nitrate, stannous chloride and antimony acetate according to molecular formula, and putting into ballGrinding the pot at a ball-milling speed of 400 rpm-1Ball milling for 8h to obtain a high-entropy oxide precursor;
the second step is that: taking a high-entropy oxide precursor to carry out annealing operation in a muffle furnace, and keeping the high-entropy oxide precursor at 500 ℃ for 10h in an air atmosphere;
the third step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-cobalt-indium high-entropy oxide powder.
The XRD representation of the bismuth-tin-antimony-cobalt-indium five-element high-entropy oxide material is shown in an attached figure 1, and the microscopic morphology is shown in a figure 2, so that the surface of the synthesized high-entropy oxide material particles is loose and porous, and the insertion and extraction of ions in the charge and discharge processes are facilitated.
The material prepared in the embodiment is used as a raw material to assemble lithium, sodium and potassium ion batteries, and the performance of the batteries is tested.
Assembling the lithium ion battery: mixing high-entropy oxide, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 8: 1:1 in NMP (N-methylpyrrolidone) for 6 hours. The mixture was uniformly coated on a copper foil by a doctor blade using a tape casting method. The operation of installing the button cell is carried out in an argon atmosphere glove box, a counter electrode is a lithium sheet, a diaphragm is made of PP (polypropylene), and electrolyte is 1mol of LiPF (lithium ion power)6in EC DMC: EMC ═ 1:1: 1).
Assembling the sodium-ion battery: mixing high-entropy oxide, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 8: 1:1 in NMP (N-methylpyrrolidone) for 6 hours. The mixture was uniformly coated on a copper foil by a doctor blade using a tape casting method. The operation of installing the button cell is carried out in an argon atmosphere glove box, the counter electrode is a sodium sheet, the diaphragm is made of glass fiber, and the electrolyte is 2mol NaPF6in DIGLYME solution.
Assembling the potassium ion battery: mixing high-entropy oxide, acetylene black and PVDF (polyvinylidene fluoride) according to a mass ratio of 8: 1:1 in NMP (N-methylpyrrolidone) for 6 hours. The mixture was uniformly coated on a copper foil by a doctor blade using a tape casting method. And (3) carrying out button cell installation operation in an argon atmosphere glove box, wherein the counter electrode is a potassium sheet, the diaphragm is made of glass fiber, and the electrolyte is 5mol of KFSI in DIGLYME solution.
The assembled lithium ion battery is subjected to battery performance test, the test results are shown in figures 3-4, and it can be found that the specific discharge capacity of the first circle is 1658mAh g-1The charging specific capacity is 1108mAh g-1At 0.5Ag-1After circulating for 80 circles under the high current density, 378mAh g is kept-1Higher specific capacity.
The battery performance test of the assembled sodium-ion battery is carried out, the test results are shown in figures 5-6, and it can be found that the specific discharge capacity of the first circle is 677mAh g-1The charging specific capacity is 545mAh g-1The first turn of coulombic efficiency is 80 percent and is 0.1Ag-1The capacity decay rate is slow, and after 50 cycles, 361mAh g is still remained-1The specific capacity of (A).
The assembled potassium ion battery is subjected to battery performance tests, the test results are shown in figures 7-8, and the test result can be found to be 0.1A g-1At a current density of (2), the initial specific charge capacity is 338mAh g-1The coulombic efficiency of the first circle is 56 percent, and the charging specific capacity after 100 circles of circulation is 334mAh g-1And excellent cycle stability is exhibited.
Example 2:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: 0.01mol of chromium nitrate, 0.01mol of antimony nitrate, 0.02mol of bismuth nitrate, 0.02mol of copper chloride, 0.02mol of tin acetate and 0.02mol of ferric nitrate are put into a ball milling tank, and the ball milling rotating speed is set to be 500r min-1Ball milling time is 12 h;
the second step is that: taking a high-entropy oxide precursor to carry out annealing operation in a muffle furnace, and keeping the high-entropy oxide precursor at 700 ℃ for 10h in an air atmosphere;
the third step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-iron-copper-chromium six-element high-entropy oxide powder.
Example 3:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: adding 0.015mol of cobalt acetate, 0.025mol of indium acetate, 0.015mol of bismuth nitrate, 0.025mol of stannous chloride and 0.02mol of antimony acetate into a centrifuge tube, adding 30mL of ultrapure water, freezing in liquid nitrogen for 0.5h, and drying in a freeze dryer for 48 h;
the second step: taking a high-entropy oxide precursor to carry out annealing operation in a muffle furnace, and keeping the high-entropy oxide precursor for 10 hours at 600 ℃ in an air atmosphere;
the third step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-cobalt-indium high-entropy oxide powder.
Example 4:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: adding 0.02mol of copper carbonate, 0.02mol of ferric nitrate, 0.02mol of bismuth acetate, 0.02mol of tin acetate and 0.02mol of antimony acetate into a centrifuge tube, adding 30mL of ultrapure water, freezing in liquid nitrogen for 0.5h, and drying in a freeze dryer for 48 h;
the second step is that: taking a high-entropy oxide precursor to carry out annealing operation in a muffle furnace, and keeping the high-entropy oxide precursor at 300 ℃ for 10h in an air atmosphere;
the third step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-iron-copper high-entropy oxide powder.
Example 5:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: adding 3.4mL (0.01mol) of tetrabutyl titanate into 60mL of ethylene glycol, placing the mixture in a beaker, and stirring to fully mix and dissolve the tetrabutyl titanate;
the second step is that: weighing 0.02mol of ferric trichloride, 0.02mol of manganese chloride, 0.015mol of bismuth nitrate, 0.015mol of antimony chloride and 0.02mol of stannous chloride, putting into the mixed solution, stirring at the rotating speed of 600r min-1Stirring for 10 hours;
the third step: putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out solvothermal reaction for 15h at 160 ℃;
the fourth step: carrying out suction filtration on the reacted suspension, taking a filter cake, cleaning the filter cake with ethanol, and then drying and grinding the filter cake to obtain bismuth tin antimony iron manganese titanium high-entropy oxide precursor powder;
the fifth step: taking a high-entropy oxide precursor to carry out annealing operation in a muffle furnace, and keeping the high-entropy oxide precursor at 500 ℃ for 18h in an air atmosphere;
and a sixth step: and grinding the material after annealing in the air to obtain the bismuth tin antimony iron manganese titanium high-entropy oxide powder.
Example 6:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: adding 3.4mL (0.01mol) of tetrabutyl titanate into 60mL of ethylene glycol, placing the mixture in a beaker, and stirring to fully mix and dissolve the tetrabutyl titanate;
the second step is that: weighing 0.015mol of magnesium carbonate, 0.015mol of nickel chloride, 0.015mol of antimony oxalate, 0.025mol of bismuth chloride and 0.02mol of tin acetate, stirring in a mixed solution at the rotating speed of 600r min-1Stirring for 10 hours;
the third step: putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out solvothermal reaction for 15h at 180 ℃;
the fourth step: carrying out suction filtration on the reacted suspension, taking a filter cake, cleaning the filter cake with ethanol, and then drying and grinding the filter cake to obtain bismuth tin antimony nickel magnesium titanium high-entropy oxide precursor powder;
the fifth step: taking a high-entropy oxide precursor to carry out annealing operation in a muffle furnace, and keeping the high-entropy oxide precursor at 700 ℃ for 18h in an air atmosphere;
and a sixth step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-nickel-magnesium-titanium high-entropy oxide powder.
Example 7:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: 60mL of ethylene glycol is measured and placed in a beaker, then 0.015mol of bismuth nitrate, 0.015mol of antimony chloride, 0.015mol of stannous chloride, 0.025mol of aluminum chloride and 0.03mol of copper chloride are weighed and placed in the beaker for stirring, 0.2mol of citric acid is added, and the rotating speed is 800r min-1Stirring for 3 hours;
the second step is that: putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out solvothermal reaction for 6 hours at 130 ℃;
the third step: placing the obtained gel in a muffle furnace for annealing operation, and keeping the temperature of 600 ℃ for 24h in an air atmosphere;
the fourth step: and grinding the material after annealing under the air to obtain the bismuth-tin-antimony-aluminum-copper high-entropy oxide powder.
Example 8:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: 60mL of ethylene glycol is measured and placed in a beaker, then 0.02mol of tin oxalate, 0.02mol of indium acetate, 0.02mol of copper sulfate, 0.02mol of bismuth chloride, 0.01mol of antimony acetate and 0.01mol of ferric chloride are weighed and placed in the beaker for stirring, 0.2mol of citric acid is added, and the rotating speed is 800r min-1Stirring for 3 hours;
the second step is that: putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out solvothermal reaction for 6 hours at 150 ℃;
the third step: placing the obtained gel in a muffle furnace for annealing operation, and keeping the temperature of the gel at 700 ℃ for 24 hours in an air atmosphere;
the fourth step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-indium-copper-iron high-entropy oxide powder.
Example 9:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: 0.02mol of stannous chloride, 0.02mol of bismuth chloride, 0.02mol of antimony chloride, 0.02mol of ferric chloride and 0.02mol of cobalt chloride are weighed and dissolved in 50ml of ultrapure water, 0.2mol of sodium carbonate is added into the ultrapure water, and the rotating speed is 1000r min-1Stirring for 8 hours;
the second step is that: carrying out suction filtration on the reacted suspension, taking a filter cake, cleaning the filter cake with ethanol, drying and grinding to obtain bismuth tin antimony iron cobalt high-entropy oxide precursor powder;
the third step: taking a high-entropy oxide precursor to carry out annealing operation in a tube furnace, and keeping the high-entropy oxide precursor at 600 ℃ for 8h in an air atmosphere; the fourth step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-iron-cobalt high-entropy oxide powder.
Example 10:
the preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony comprises the following steps:
the first step is as follows: 0.03mol of magnesium acetate, 0.03mol of chromium nitrate, 0.02mol of bismuth nitrate, 0.01mol of tin acetate and 0.01mol of antimony chloride are weighed and dissolved in 50ml of ultrapure water, 0.2mol of sodium carbonate is added into the ultrapure water, and the rotating speed is 1000r min-1Stirring for 8 hours;
the second step is that: carrying out suction filtration on the reacted suspension, taking a filter cake, cleaning the filter cake with ethanol, and then drying and grinding the filter cake to obtain bismuth tin antimony magnesium chromium high-entropy oxide precursor powder;
the third step: taking a high-entropy oxide precursor to carry out annealing operation in a tube furnace, and keeping the high-entropy oxide precursor at 500 ℃ for 8h in an air atmosphere;
the fourth step: and grinding the material after annealing in the air to obtain the bismuth-tin-antimony-magnesium-chromium high-entropy oxide powder.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. The high-entropy oxide cathode energy storage material containing bismuth, tin and antimony is characterized in that: five-element or above multi-element high-entropy oxide is formed by taking two or more metal salts of nickel, cobalt, manganese, copper, chromium, iron, indium, germanium, magnesium, aluminum, zinc, molybdenum, tungsten, vanadium and titanium and one or more metal salts of bismuth, tin and antimony as raw materials; wherein the proportion of each metal element is 5-35%, the sum of the atomic proportions of all the metal elements is 1, five-element or above multi-element high-entropy oxide precursors are synthesized by one of the methods of physical ball milling, freeze drying, solvent heating, sol-gel or coprecipitation, and then the target product is obtained by annealing under the air.
2. The preparation method of the high-entropy oxide cathode energy storage material containing bismuth, tin and antimony is characterized by comprising the following steps of:
the first step is as follows: preparing a high-entropy oxide precursor by using five or more than five metal salts as raw materials by one of methods of physical ball milling, freeze drying, solvent heating, sol-gel or coprecipitation;
the second step: and (3) placing the high-entropy oxide precursor in an annealing furnace to carry out annealing treatment in the air, and grinding the material after the annealing is finished to obtain the high-entropy oxide material.
3. The preparation method of the bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material according to claim 2, characterized by comprising the following steps: the physical ball milling method in the first step is that the ball milling rotating speed is 400--1The ball milling time is 5-15 h.
4. The preparation method of the bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material according to claim 2, characterized by comprising the following steps: in the first step, the freeze drying method comprises the steps of adding metal salt into a centrifuge tube, adding 30mL of ultrapure water, putting into liquid nitrogen for freezing for 0.5h, and then putting into a freeze dryer for drying for 48 h.
5. The preparation method of the bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material according to claim 2, characterized by comprising the following steps: the solvothermal method in the first step is to prepare a mixed solution of tetrabutyl titanate and ethylene glycol, add metal salt, stir, perform solvothermal reaction at the temperature of 100-200 ℃, the reaction time is 10-20h, and perform suction filtration, cleaning, drying and grinding after the reaction is finished.
6. The preparation method of the bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material according to claim 2, characterized by comprising the following steps: in the first step, the sol-gel method is to add metal salt and citric acid with the molar mass of two parts of metal salt into 60ml of ethylene glycol solution, stir for 3 hours, and then carry out solvothermal reaction at the temperature of 130-150 ℃, wherein the reaction time is 6 hours.
7. The preparation method of the bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material according to claim 2, characterized by comprising the following steps: the coprecipitation method in the first step is to dissolve metal salt in 50ml of ultrapure water, add two parts of sodium carbonate with the molar mass of the metal salt, and rotate at the rotating speed of 1000r min-1Stirring for 8h, carrying out suction filtration after the reaction is finished, and cleaning, drying and grinding a filter cake by using ethanol.
8. The preparation method of the bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material according to claim 2, characterized by comprising the following steps: the metal salt in the first step comprises an acetate, a nitrate, a chloride, a carbonate, an oxalate or a sulfate.
9. The preparation method of the bismuth-tin-antimony-containing high-entropy oxide anode energy storage material as claimed in claim 2, is characterized in that: in the second step, the annealing temperature is 300-700 ℃, and the annealing time is 0.5-48 h.
10. The application of the bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material disclosed by claim 1 in negative electrode materials of potassium, sodium and lithium ion batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210099616.3A CN114530590B (en) | 2022-01-27 | 2022-01-27 | Bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210099616.3A CN114530590B (en) | 2022-01-27 | 2022-01-27 | Bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114530590A true CN114530590A (en) | 2022-05-24 |
| CN114530590B CN114530590B (en) | 2024-03-12 |
Family
ID=81622107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210099616.3A Active CN114530590B (en) | 2022-01-27 | 2022-01-27 | Bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114530590B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261662A (en) * | 2022-08-12 | 2022-11-01 | 陕西科技大学 | High-entropy alloy CuSnZnAlCd/C carbon-based composite material and preparation method and application thereof |
| CN115594235A (en) * | 2022-11-29 | 2023-01-13 | 广西师范大学（Cn） | Preparation method and application of sodium-ion battery negative electrode material |
| CN116396073A (en) * | 2023-03-24 | 2023-07-07 | 常州大学 | Dielectric material for ballast water treatment high-voltage pulse and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080003503A1 (en) * | 2006-06-09 | 2008-01-03 | Canon Kabushiki Kaisha | Powder material, electrode structure using the powder material, and energy storage device having the electrode structure |
| US20110236747A1 (en) * | 2010-03-29 | 2011-09-29 | Kan-Sen Chou | Composite material for negative electrode, method for fabricating the same and electrochemical device using the same |
| US20150357646A1 (en) * | 2012-03-28 | 2015-12-10 | Sharp Laboratories Of America, Inc. | Sodium and Potassium Ion Batteries with Halogen Salts |
| WO2018094783A1 (en) * | 2016-11-23 | 2018-05-31 | 清华大学 | Silicon-based and tin-based composite particle for lithium ion battery, preparation method therefor, and negative electrode and lithium ion battery having same |
| CN110289416A (en) * | 2019-06-26 | 2019-09-27 | 中南大学 | A kind of preparation method of anode material of lithium-ion battery bismuth molybdenum bimetallic sulfide |
| CN112599749A (en) * | 2020-12-18 | 2021-04-02 | 安徽工业大学 | High-entropy oxide lithium ion battery cathode material with high conductivity and preparation method thereof |
| CN113346062A (en) * | 2021-06-01 | 2021-09-03 | 南京邮电大学 | Multiphase composite titanium-based negative electrode material and preparation method thereof |
| CN113809316A (en) * | 2021-09-17 | 2021-12-17 | 广东省国研科技研究中心有限公司 | Ternary alloy negative electrode active material and preparation method and application thereof |
-
2022
- 2022-01-27 CN CN202210099616.3A patent/CN114530590B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080003503A1 (en) * | 2006-06-09 | 2008-01-03 | Canon Kabushiki Kaisha | Powder material, electrode structure using the powder material, and energy storage device having the electrode structure |
| US20110236747A1 (en) * | 2010-03-29 | 2011-09-29 | Kan-Sen Chou | Composite material for negative electrode, method for fabricating the same and electrochemical device using the same |
| US20150357646A1 (en) * | 2012-03-28 | 2015-12-10 | Sharp Laboratories Of America, Inc. | Sodium and Potassium Ion Batteries with Halogen Salts |
| WO2018094783A1 (en) * | 2016-11-23 | 2018-05-31 | 清华大学 | Silicon-based and tin-based composite particle for lithium ion battery, preparation method therefor, and negative electrode and lithium ion battery having same |
| CN110289416A (en) * | 2019-06-26 | 2019-09-27 | 中南大学 | A kind of preparation method of anode material of lithium-ion battery bismuth molybdenum bimetallic sulfide |
| CN112599749A (en) * | 2020-12-18 | 2021-04-02 | 安徽工业大学 | High-entropy oxide lithium ion battery cathode material with high conductivity and preparation method thereof |
| CN113346062A (en) * | 2021-06-01 | 2021-09-03 | 南京邮电大学 | Multiphase composite titanium-based negative electrode material and preparation method thereof |
| CN113809316A (en) * | 2021-09-17 | 2021-12-17 | 广东省国研科技研究中心有限公司 | Ternary alloy negative electrode active material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| WOLFGANG BREHM 等: "Reactive and Nonreactive Ball Milling of Tin-Antimony (Sn-Sb) Composites and Their Use as Electrodes for Sodium-Ion Batteries with Glyme Electrolyte", 《ENERGY TECHNOLOGY》, vol. 7, pages 269 - 270 * |
| 刘小文 等: "锡盐共沉淀法净化铜电解液工艺研究", 《矿冶工程》, vol. 41, no. 2, pages 102 - 105 * |
| 郑颖 等: "锂离子蓄电池锡基复合负极材料的研究", 《电源技术》, vol. 30, no. 8, pages 645 - 648 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261662A (en) * | 2022-08-12 | 2022-11-01 | 陕西科技大学 | High-entropy alloy CuSnZnAlCd/C carbon-based composite material and preparation method and application thereof |
| CN115261662B (en) * | 2022-08-12 | 2023-05-26 | 陕西科技大学 | High-entropy alloy CuSnZnAlCD/C carbon-based composite material and preparation method and application thereof |
| CN115594235A (en) * | 2022-11-29 | 2023-01-13 | 广西师范大学（Cn） | Preparation method and application of sodium-ion battery negative electrode material |
| CN115594235B (en) * | 2022-11-29 | 2023-11-24 | 广西师范大学 | Preparation method and application of negative electrode material of sodium ion battery |
| CN116396073A (en) * | 2023-03-24 | 2023-07-07 | 常州大学 | Dielectric material for ballast water treatment high-voltage pulse and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114530590B (en) | 2024-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111697210B (en) | Sodium ion battery multi-element positive electrode material and preparation method thereof | |
| CN114530590B (en) | Bismuth-tin-antimony-containing high-entropy oxide negative electrode energy storage material, and preparation method and application thereof | |
| CN114883522B (en) | High-entropy-like multi-element layered transition metal oxide positive electrode material, and preparation method and application thereof | |
| CN103151508B (en) | Mix composite cathode material for lithium ion cell of lanthanum lithium titanate and preparation method thereof | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN108933237B (en) | Preparation method and application of lithium ion battery positive electrode material | |
| CN110589791B (en) | Preparation method of tin-doped titanium pyrophosphate | |
| CN114566632B (en) | Positive electrode material for sodium ion battery and preparation method thereof | |
| CN101847717A (en) | Preparation method of lithium titanate composite negative electrode materials used by lithium ion batteries | |
| CN113675394B (en) | Potassium ion battery positive electrode material, preparation method and potassium ion battery | |
| CN115057485A (en) | Non-metal boron-doped layered oxide sodium ion battery positive electrode material and preparation method and application thereof | |
| CN102969493B (en) | For the preparation method of the negative material of non-aqueous secondary batteries, non-aqueous secondary batteries negative pole and non-aqueous secondary batteries | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN103066260B (en) | For the negative material and preparation method thereof of non-aqueous secondary batteries, non-aqueous secondary batteries negative pole and non-aqueous secondary batteries | |
| CN103545508B (en) | A kind of lithium iron borate anode material of lithium ion battery and its preparation method | |
| CN114590838B (en) | Amorphous metal sulfide coated modified binary manganese-based sodium electro-precursor and preparation method thereof | |
| CN116417598A (en) | Iron-based polyanion type sodium ion battery positive electrode material and preparation method thereof | |
| CN115010186A (en) | High-capacity oxygen valence-variable sodium ion battery positive electrode material and preparation method thereof | |
| CN112777611B (en) | Rhombohedral phase Prussian blue derivative and preparation method and application thereof | |
| CN113363460A (en) | Preparation method of lithium ion battery negative electrode material zinc nickelate bimetallic oxide | |
| CN102983318B (en) | Material for negative electrode of non-aqueous secondary battery, preparation method of material, non-aqueous secondary battery and negative electrode thereof | |
| CN114824243B (en) | Preparation method of Co-doped niobium oxide anode material capable of being rapidly charged and deep sea energy storage battery thereof | |
| CN114256460B (en) | Large-scale preparation of high-crystallization Prussian blue analogues for sodium ion battery by using salt water-in-water microreactor principle | |
| CN114597370B (en) | Air-stable high-voltage long-cycle-life sodium ion battery positive electrode material and preparation method thereof | |
| CN115504525A (en) | P2 type layered transition metal oxide and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |