CN116722131A - Low-entropy antimony-based binary superfine nanocrystalline oxide negative electrode material and preparation method thereof - Google Patents
Low-entropy antimony-based binary superfine nanocrystalline oxide negative electrode material and preparation method thereof Download PDFInfo
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- CN116722131A CN116722131A CN202310726372.1A CN202310726372A CN116722131A CN 116722131 A CN116722131 A CN 116722131A CN 202310726372 A CN202310726372 A CN 202310726372A CN 116722131 A CN116722131 A CN 116722131A
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- antimony
- entropy
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- metal oxide
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- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 53
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 63
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 63
- 238000000498 ball milling Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000001816 cooling Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 7
- 239000011777 magnesium Substances 0.000 claims abstract description 7
- 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 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 239000011135 tin Substances 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 7
- 239000010937 tungsten Substances 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000137 annealing Methods 0.000 claims abstract 2
- 239000010405 anode material Substances 0.000 claims description 30
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 16
- 229910001414 potassium ion Inorganic materials 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000007581 slurry coating method Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 229910000410 antimony oxide Inorganic materials 0.000 abstract 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 abstract 1
- 230000005476 size effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 description 4
- UFIKNOKSPUOOCL-UHFFFAOYSA-N antimony;cobalt Chemical compound [Sb]#[Co] UFIKNOKSPUOOCL-UHFFFAOYSA-N 0.000 description 4
- TUFZVLHKHTYNTN-UHFFFAOYSA-N antimony;nickel Chemical compound [Sb]#[Ni] TUFZVLHKHTYNTN-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- PEEDYJQEMCKDDX-UHFFFAOYSA-N antimony bismuth Chemical compound [Sb].[Bi] PEEDYJQEMCKDDX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 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 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G30/00—Compounds of antimony
- C01G30/004—Oxides; Hydroxides; Oxyacids
- C01G30/005—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a low-entropy antimony-based binary superfine nanocrystalline oxide negative electrode material and a preparation method thereof, wherein the material is a low-entropy antimony-based binary superfine nanocrystalline metal oxide material composed of antimony and one impurity element of nickel, cobalt, manganese, copper, chromium, iron, tin, indium, germanium, magnesium, bismuth, aluminum, zinc, molybdenum, tungsten, vanadium, silicon or titanium, and the like, and the impurity element accounts for 10-50% of the total metal element mole percent; the preparation method comprises the steps of ball milling, mixing, cooling and sintering, ball milling and mixing antimony and impurity metal salt, then placing the mixed salt in a muffle furnace for annealing, heating to 350-600 ℃ at a speed of 5-10 ℃/s, cooling to 200 ℃ at a speed of 0.05-10 ℃/s, and cooling to room temperature along with the furnace. The invention can not only keep the high specific capacity of the antimony oxide, but also obtain excellent circulation stability by utilizing the nanometer size effect of the superfine nanocrystalline and the defect-rich mesoporous structure to cooperatively relieve the internal stress generated by huge volume change in the charge and discharge process.
Description
Technical Field
The invention discloses a low-entropy antimony-based binary superfine nanocrystalline oxide anode material and a preparation method thereof, and belongs to the technical field of energy conservation and environmental protection.
Background
Under the large background of carbon peak and carbon neutralization, the proportion of renewable energy sources is gradually increased, and the new energy industry is vigorously developed. However, the new energy system is limited in practical application due to its volatility and intermittence. The large-scale energy storage system can just meet the requirement of the new energy system on flexibility. Therefore, the energy storage technology realizes the large-scale grid-connected use of renewable energy sources, and a technical path for promoting the low-carbonization transformation of the energy sources is expected in the industry. At present, commercial Lithium Ion Batteries (LIBs) are limited by low natural resource abundance of metal lithium, so that the price of raw materials is increased all the way, and great challenges are brought to further sustainable development of the lithium ion batteries. In contrast, potassium resources are abundant and widely distributed, with a content of 1.5wt% in the crust (lithium resources content of only 0.0017 wt%), which brings great potential for low-cost large-scale commercial applications. In addition, the potassium ion battery also has the advantages of low standard reduction potential, smaller stokes radius and the like by virtue of the potassium cathode, and is considered as another potential low-cost energy storage system with high voltage and high multiplying power after the lithium ion battery, so that the potassium ion battery is attracting more attention in the industry.
Graphite is the most widely used negative electrode material of the alkali metal ion battery, and is beneficial to the characteristics of good conductivity/heat property, various structures, low price, obvious charge and discharge platform and the like, but has the problems of low lithium intercalation potential, easy dendrite generation, low specific capacity and the like, so the research and development of the negative electrode material of the alkali metal ion battery with excellent performance, quick preparation and easy large-scale commercial application is needed. In contrast, metal oxide has excellent ion removing/inserting capability, theoretical specific capacity is generally higher, meanwhile, the metal oxide has the advantages of higher safety, higher stacking density, easiness in preparation and the like, however, the traditional metal oxide anode material generally undergoes a complex phase change process and huge volume change in the charge and discharge process, and the structure caused by the complex phase change process and the huge volume change is seriously collapsed, so that the traditional metal oxide anode material is poor in cycle stability.
The oxide negative electrode material has large volume change in the charge/discharge process, complex phase change process, and the new surface of the active material is always re-exposed after being crushed, and the solid electrolyte interface film is repeatedly formed/peeled off, so that the electrolyte and the active material are rapidly consumed, and the capacity is rapidly attenuated.
Disclosure of Invention
Aiming at the defects or shortcomings of the prior art, the invention provides a low-entropy antimony-based binary ultrafine nanocrystalline oxide negative electrode material and a preparation method thereof, and the method solves the technical problems of low capacity, coarse grains, poor multiplying power performance, poor electric conductivity, unstable cycle performance and the like of the existing potassium ion battery negative electrode material in the prior art. The low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material provided by the invention becomes one of candidate materials with great potential for commercial potassium ion battery anode materials due to the advantages of higher specific capacity, better multiplying power performance, excellent cycle stability, higher bulk density, simple batch preparation method, rich raw materials and the like. The invention can prepare the low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material, and can be applied to the anode of other alkali metal (lithium and sodium) ion batteries.
The technical scheme adopted for solving the technical problems is as follows: the low-entropy antimony-based binary ultrafine nanocrystalline metal oxide negative electrode material is small-size low-entropy antimony-based binary ultrafine nanocrystalline metal oxide formed by oxidizing bismuth element and one element of doping elements nickel, cobalt, manganese, copper, chromium, iron, tin, indium, germanium, magnesium, bismuth, aluminum, zinc, molybdenum, tungsten, vanadium, silicon or titanium and the like in the molar ratio of 10-50% of impurity elements to total metal elements; the method comprises the steps of uniformly mixing the two element metal salts through a physical ball milling method to prepare precursor powder, and cooling and sintering the precursor powder under air to obtain a target product.
The invention also provides a preparation method of the low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material, which comprises the following steps:
step 1: preparing a low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material precursor by taking metal salt of an antimony element and metal salt of one element of doped elements of nickel, cobalt, manganese, copper, chromium, iron, tin, indium, germanium, magnesium, bismuth, aluminum, zinc, molybdenum, tungsten, vanadium, silicon or titanium and the like as raw materials by a physical ball milling method;
step 2: and (3) placing the precursor in a muffle furnace to perform cooling sintering treatment under air, and grinding the material after cooling sintering to obtain the low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material.
As a preferred technical scheme of the invention: the physical ball milling method in the step 1 is that the ball milling rotating speed is 400-600rmin -1 Ball milling time is 5-10h.
As a preferred technical scheme of the invention: the metal salt in the step 1 comprises nitrate, chlorate, carbonate, acetate, oxalate or sulfate.
As a preferred technical scheme of the invention: the cooling sintering condition in the step 2 is air atmosphere, the temperature is increased to 350-600 ℃ at the speed of 5-10 ℃/s, namely, the temperature is reduced to 200 ℃ at the speed of 0.05-10 ℃/s, and then the furnace cooling is carried out to the room temperature.
As a preferred technical scheme of the invention: the potassium ion battery is assembled by mixing a low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material, acetylene black and CMC (carboxymethyl cellulose) according to the mass ratio of 7:2:1 in deionized water for 3-10h; uniformly coating the mixture on a copper foil by using a doctor blade through a tape casting method; button cell assembly operation is carried out in an argon atmosphere glove box, the model number of the button cell is CR2032, the counter electrode is a potassium plate, the diaphragm is made of glass fiber, and the electrolyte is 5mol KFSI in DIGLYME.
According to the invention, the main active material antimony element and the metal salt of one element of doping elements nickel, cobalt, manganese, copper, chromium, iron, tin, indium, germanium, magnesium, bismuth, aluminum, zinc, molybdenum, tungsten, vanadium, silicon or titanium are uniformly mixed by a physical ball milling method as raw materials, and then the raw materials are cooled and sintered in an air atmosphere to obtain the corresponding low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material. In addition, due to the cooperation of the defect-rich mesoporous structure, the electrolyte is beneficial to rapid diffusion, the volume expansion of the material in the electrochemical circulation process is relieved, enough active sites are ensured, and the specific capacity is improved. The pores increase the contact area between the electrolyte and the electrode, and shorten K + Is beneficial to K + Can relieve the strain caused by volume change in the electrochemical reaction process, and has better structural stability.
The beneficial effects are that:
1. the small-size nanocrystal structure of the invention has higher specific capacity and excellent structural stability.
2. The low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material has good conductivity and good multiplying power performance.
3. The small-size nano crystal structure can relieve the volume expansion of the electrode, thereby inhibiting the huge volume change of the oxide electrode and stabilizing the structure.
4. The low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material is well matched with electrolyte, and can form a stable solid electrolyte interface.
5. The invention has the advantages of synergistic effect of the defect-rich mesoporous structure, contribution to rapid diffusion of electrolyte, shortening of ion transmission path and effective improvement of specific capacity. The mesoporous increases the contact area of the electrolyte and the electrode, relieves the strain, effectively inhibits the aggregation and crack expansion of particles in the charge and discharge process of the low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material, ensures the integrity of the electrode, and has good cycle performance and stable structure.
6. The preparation method of the invention has the advantages of simplicity, short period, easily obtained raw materials, low cost and huge industrialization application value.
7. The low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide anode prepared by a physical ball milling wet milling method is used as a potassium ion battery anode material, and is 0.1-0.1A g -1 At a current density of 776mAh g in specific discharge capacity at the first turn -1 The specific charge capacity is 370mAh g -1 After 800 circles, 450mAh g is also maintained -1 Is a high specific capacity of (a).
Drawings
FIG. 1 is an XRD pattern of a low-entropy bismuth-antimony binary ultra-fine nanocrystalline metal oxide anode material prepared by ball milling according to the invention.
Fig. 2 is an SEM image of the low-entropy bismuth-antimony binary ultra-fine nanocrystalline metal oxide anode material prepared by ball milling according to the invention.
Identification description: (a) And a microscopic morphology diagram of the low-entropy bismuth-antimony binary superfine nanocrystalline oxide with the magnification of 30K is shown. (b) And a microscopic morphology diagram of the low-entropy bismuth-antimony binary superfine nanocrystalline oxide with the magnification of 120K is shown.
FIG. 3 is a graph showing charge and discharge of the low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide anode material prepared by ball milling as a potassium ion battery anode.
FIG. 4 is a graph showing the long cycle performance of the low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide anode material prepared by ball milling according to the invention as a potassium ion battery anode.
FIG. 5 is a cooling sintering diagram of the low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide anode material prepared by ball milling according to the invention.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the accompanying drawings and specific examples, which are only for illustrating the present invention, and the present invention is not limited to the following examples. All modifications and equivalent substitutions to the technical proposal of the invention are included in the protection scope of the invention without departing from the spirit and scope of the technical proposal of the invention.
In the general implementation mode of the low-entropy bismuth-antimony binary ultra-fine nanocrystalline metal oxide anode material, the low-entropy bismuth-antimony binary ultra-fine nanocrystalline metal oxide can obtain a diffraction curve through X-ray diffraction (XRD), and phase information is obtained through comparison with a standard PDF card. The microscopic morphology was observed by a field emission Scanning Electron Microscope (SEM). The low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material, acetylene black and CMC are mixed according to the mass ratio of 7:2:1 in deionized water for 4-10h; the mixture was uniformly coated on a copper foil with a doctor blade by a casting method, the slurry coating thickness was 50 μm, and the button cell mounting operation was performed in an argon atmosphere glove box. And (3) performing charge and discharge tests on the button cell to obtain a charge and discharge curve and a long cycle curve of the button cell.
In the following examples, a physical ball milling method is adopted to uniformly mix metal salt of antimony element with metal salt of one impurity element of nickel, cobalt, manganese, copper, chromium, iron, tin, indium, germanium, magnesium, bismuth, aluminum, zinc, molybdenum, tungsten, vanadium, silicon or titanium and the like, a low-entropy antimony-based binary superfine nanocrystalline metal oxide material precursor is formed after drying, then the low-entropy antimony-based binary superfine nanocrystalline metal oxide material is produced by cooling and sintering in air, and a potassium ion battery cathode is manufactured by using the material, and relevant tests are carried out.
Example 1
The invention provides a preparation method of a low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide anode, which comprises the following steps:
step 1: according to the formulaWeighing bismuth nitrate and antimony acetate with equal molar weight, putting the bismuth nitrate and the antimony acetate into a ball milling tank, and setting the ball milling rotating speed to 300rmin -1 Ball milling for 5h to obtain a low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide negative electrode precursor;
step 2: taking a low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide anode precursor, performing cooling sintering operation in a muffle furnace, and heating to 500 ℃ at a speed of 5-10 ℃/s, namely cooling to 200 ℃ at a speed of 0.05 ℃/s, and cooling to room temperature along with the furnace;
step 3: grinding the material annealed in the air to obtain the low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide negative electrode material powder.
XRD characterization of the low-entropy bismuth antimony binary ultra-fine nanocrystalline metal oxide cathode is shown in figure 1, and microscopic morphology is shown in figure 2, so that the synthesized low-entropy bismuth antimony binary ultra-fine nanocrystalline metal oxide cathode has extremely small particles, lamellar and loose and porous surface, and is beneficial to ion intercalation and deintercalation in the charge and discharge process.
The material prepared in the embodiment is used as a raw material to assemble a potassium ion battery, and the battery performance is tested.
And (3) assembling a potassium ion battery: the low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide cathode, acetylene black and CMC (carboxymethyl cellulose) are mixed according to the mass fraction ratio of 7:2:1 in deionized water for 6h. The mixture was uniformly coated on a copper foil using a doctor blade by a casting method. Button cell assembly operation is carried out in an argon atmosphere glove box, the model number of the button cell is CR2032, the counter electrode is a potassium plate, the diaphragm is made of glass fiber, and the electrolyte is 5mol KFSI in DIGLYME.
The assembled potassium ion battery was subjected to a battery performance test, and the test results are shown in fig. 3 and 4. As shown in FIG. 3, at 0.1A g -1 According to the discharge curve of voltage reduction, the initial-turn discharge specific capacity of the low-entropy bismuth-antimony binary ultra-fine nanocrystalline metal oxide anode is 776mAh g -1 According to the charging curve of voltage rise, the initial charge specific capacity of the low-entropy bismuth-antimony binary superfine nanocrystalline metal oxide anode is 338mAh g -1 . As shown in figure 4, the low-entropy bismuth-antimony binary superfine nanoThe nano-crystal metal oxide cathode also maintains 450mAh g after 800 times of circulation -1 Is a high specific capacity of (a).
Example 2
The invention provides a preparation method of a low-entropy cobalt-antimony binary superfine nanocrystalline metal oxide anode, which comprises the following steps:
step 1: weighing cobalt carbonate and antimony nitrate with equal molar weight according to molecular formula, putting the cobalt carbonate and the antimony nitrate into a ball milling tank, and setting the ball milling rotating speed to be 500rmin -1 Ball milling for 6h to obtain a low-entropy cobalt-antimony binary superfine nanocrystalline metal oxide anode precursor;
step 2: taking a low-entropy cobalt-antimony binary superfine nanocrystalline metal oxide anode precursor, performing cooling sintering operation in a muffle furnace, and heating to 400 ℃ at a speed of 5 ℃/s, namely cooling to 200 ℃ at a speed of 0.05 ℃/s, and cooling to room temperature along with the furnace;
step 3: grinding the material annealed in the air to obtain the low-entropy cobalt-antimony binary superfine nanocrystalline metal oxide negative electrode powder.
Example 3
The invention provides a preparation method of a low-entropy antimony-nickel binary superfine nanocrystalline metal oxide anode, which comprises the following steps:
step 1: weighing equimolar amount of nickel acetate and antimony acetate according to molecular formula, putting into a ball milling tank, and setting the ball milling rotation speed to be 500rmin -1 Ball milling for 8h to obtain a low-entropy antimony-nickel binary superfine nanocrystalline metal oxide cathode;
step 2: taking a low-entropy antimony-nickel binary superfine nanocrystalline metal oxide anode precursor, performing cooling sintering operation in a muffle furnace, and heating to 400 ℃ at a speed of 5 ℃/s, namely cooling to 200 ℃ at a speed of 0.05 ℃/s, and cooling to room temperature along with the furnace;
step 3: grinding the material annealed in the air to obtain the low-entropy antimony-nickel binary superfine nanocrystalline metal oxide negative electrode powder.
Example 4
The invention provides a preparation method of a low-entropy antimony tin binary superfine nanocrystalline metal oxide anode, which comprises the following steps:
step 1: weighing equal molar weight of tin nitrate and antimony acetate according to molecular formula, putting the tin nitrate and the antimony acetate into a ball milling tank, and setting the ball milling rotating speed to be 500rmin -1 Ball milling for 6h to obtain a low-entropy antimony tin binary superfine nanocrystalline metal oxide negative electrode precursor;
step 2: taking a low-entropy antimony tin binary superfine nanocrystalline metal oxide anode precursor, performing cooling sintering operation in a muffle furnace, and heating to 400 ℃ at a speed of 8 ℃/s, namely cooling to 200 ℃ at a speed of 0.1 ℃/s, and cooling to room temperature along with the furnace;
step 3: grinding the material annealed in the air to obtain the low-entropy antimony tin binary superfine nanocrystalline metal oxide negative electrode powder.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (7)
1. A low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material is characterized in that: the material is an ultra-fine nanocrystalline metal oxide material formed by mixing antimony element and one of doping elements nickel, cobalt, manganese, copper, chromium, iron, tin, indium, germanium, magnesium, bismuth, aluminum, zinc, molybdenum, tungsten, vanadium, silicon or titanium and the like, wherein the mole ratio of the antimony element to the impurity element accounts for 10-50% of the mole percentage of the total metal element, a precursor of the low-entropy binary ultra-fine nanocrystalline oxide negative electrode material is synthesized by a physical ball milling method, and then the precursor is cooled and sintered under air to obtain a target product.
2. The preparation method of the low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material is characterized by comprising the following steps of:
step 1: preparing a low-entropy antimony-based binary superfine nanocrystalline metal oxide anode material precursor by taking metal salt of an antimony element and metal salt of one element of doped elements of nickel, cobalt, manganese, copper, chromium, iron, tin, indium, germanium, magnesium, bismuth, aluminum, zinc, molybdenum, tungsten, vanadium, silicon or titanium and the like as raw materials by a physical ball milling method;
step 2: and (3) placing the precursor of the low-entropy antimony-based binary superfine nanocrystalline metal oxide negative electrode material into an annealing furnace, cooling and sintering in the air, and grinding the material after cooling and sintering to obtain the low-entropy antimony-based binary superfine nanocrystalline metal oxide negative electrode material.
3. The method for preparing the low-entropy antimony-based binary ultrafine nanocrystalline metal oxide anode material according to claim 2, which is characterized in that: the physical ball milling method in the step 1 is that the ball milling rotating speed is 400-600r min -1 Ball milling time is 5-10h.
4. The method for preparing the low-entropy antimony-based binary ultrafine nanocrystalline metal oxide anode material according to claim 2, which is characterized in that: the metal salt in step 1 includes nitrate, chlorate, carbonate, acetate, oxalate or sulfate.
5. The method for preparing a low-entropy antimony-based binary ultra-fine nanocrystalline metal oxide anode material according to claim 2, wherein the cooling sintering treatment conditions in step 2 are as follows: in the air atmosphere, the temperature is increased to 350-600 ℃ at the speed of 5-10 ℃/s, namely, the temperature is reduced to 200 ℃ at the speed of 0.05-10 ℃/s, and then the temperature is cooled to the room temperature along with the furnace.
6. Use of the low-entropy antimony-based binary ultra-fine nanocrystalline metal oxide anode material according to claim 1 in a potassium ion battery anode material, characterized in that: the low-entropy antimony-based binary ultrafine nanocrystalline metal oxide negative electrode material is applied to a potassium ion battery negative electrode, and the potassium ion battery assembly process is that the low-entropy antimony-based binary ultrafine nanocrystalline metal oxide negative electrode material, acetylene black and CMC are mixed according to the mass ratio of 7:2:1 in deionized water for 4-10h; uniformly coating the mixture on a copper foil by using a doctor blade by using a tape casting method, wherein the thickness of the slurry coating is 50 mu m; button cell loading operations were performed in an argon atmosphere glove box.
7. The application of the low-entropy antimony-based binary ultrafine nanocrystalline metal oxide negative electrode material in the potassium ion battery negative electrode material according to claim 6, wherein the button battery model is CR2032, the counter electrode is a potassium plate, the diaphragm is made of glass fiber, and the electrolyte is 5mol KFSI in DIGLYME.
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