CN116722141A - Coating material of sodium ion battery anode material, anode material and preparation method of anode material - Google Patents
Coating material of sodium ion battery anode material, anode material and preparation method of anode material Download PDFInfo
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- CN116722141A CN116722141A CN202310735380.2A CN202310735380A CN116722141A CN 116722141 A CN116722141 A CN 116722141A CN 202310735380 A CN202310735380 A CN 202310735380A CN 116722141 A CN116722141 A CN 116722141A
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- positive electrode
- coating
- sodium ion
- electrode material
- ion battery
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- 239000011248 coating agent Substances 0.000 title claims abstract description 131
- 238000000576 coating method Methods 0.000 title claims abstract description 131
- 239000000463 material Substances 0.000 title claims abstract description 117
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 62
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000010405 anode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 140
- 239000011162 core material Substances 0.000 claims abstract description 94
- 239000007774 positive electrode material Substances 0.000 claims abstract description 91
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims description 75
- 239000011777 magnesium Substances 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- 238000000137 annealing Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012298 atmosphere Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 16
- 239000011247 coating layer Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 238000007580 dry-mixing Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 5
- 238000005253 cladding Methods 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 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 abstract description 28
- 239000003792 electrolyte Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000003628 erosive effect Effects 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 53
- 239000002243 precursor Substances 0.000 description 26
- 239000007787 solid Substances 0.000 description 26
- 238000001816 cooling Methods 0.000 description 25
- 238000007873 sieving Methods 0.000 description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- 238000012360 testing method Methods 0.000 description 19
- -1 magnesium sodium manganese sulfate Chemical compound 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- 238000001354 calcination Methods 0.000 description 14
- 208000028659 discharge Diseases 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000001514 detection method Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 11
- 238000005303 weighing Methods 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- RDPLOLUNEKBWBR-UHFFFAOYSA-L magnesium;sodium;sulfate Chemical compound [Na+].[Mg+2].[O-]S([O-])(=O)=O RDPLOLUNEKBWBR-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002103 nanocoating Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229910004563 Na2Fe2 (SO4)3 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013256 coordination polymer Substances 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229920000447 polyanionic polymer Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- YPPMLCHGJUMYPZ-UHFFFAOYSA-L sodium;iron(2+);sulfate Chemical compound [Na+].[Fe+2].[O-]S([O-])(=O)=O YPPMLCHGJUMYPZ-UHFFFAOYSA-L 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/12—Preparation of double sulfates of magnesium with sodium or potassium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- 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
- C01P2006/10—Solid density
-
- 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
- C01P2006/12—Surface area
-
- 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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a coating material of a sodium ion battery anode material, the anode material and a preparation method thereof, wherein the coating material comprises Na 6 Mg a Mn b N c (SO 4 ) 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a+b+c=1, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 0.2, and N is one or more than two of transition metal elements. By coating the surface of the core material with a layer of coating material with stable properties, the core material and electrolysis can be avoidedThe liquid is in direct contact, so that the erosion of the electrolyte to the core material is relieved, the structural stability of the core material is improved, and the cycle performance of the core material is improved. In addition, the coating material disclosed by the invention belongs to high-sodium sulfate, and can also prevent sodium ions in the core material from enriching to the surface of the core material, inhibit the formation of residual sodium phase on the surface of the positive electrode material and keep the electrochemical performance of the sodium ion battery.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a coating material of a positive electrode material of a sodium ion battery, the positive electrode material and a preparation method of the positive electrode material.
Background
The lithium ion battery has the characteristics of high energy density, good cycle performance, high and stable working voltage platform and the like, so the lithium ion battery has wide application in the fields of new energy automobiles, energy storage and the like. However, due to the influence of factors such as limited storage of lithium ore resources, the price fluctuation of the precursor lithium carbonate serving as the positive electrode material of the lithium battery is large, and the rapid development of the precursor lithium carbonate in the aspect of energy storage, especially in the field of power batteries, is limited.
Under the background, the sodium ion battery has been widely studied and rapidly developed in recent years due to the advantages of excellent low-temperature and high-temperature performance, good safety, rich sodium sources, low cost and the like.
The positive electrode material is an important component of the sodium ion battery and plays a key role in the performance of the battery. Sodium ion positive electrode materials are generally classified into layered transition metal oxides, prussian blue, polyanion compounds, and the like, wherein the layered transition metal oxides have the advantages of high energy density, multiple types, easy synthesis, and the like, and are considered as sodium ion battery positive electrode materials most likely to realize industrialization.
When the layered transition metal oxide is used as a positive electrode material, the layered transition metal oxide is easily corroded by electrolyte in the process of charge and discharge cycles, and sodium ions in the positive electrode material are enriched to the surface in the process of charge and discharge cycles, so that a surface residual sodium phase is generated, and the electrochemical performance of the battery is reduced.
Disclosure of Invention
The invention aims to provide a coating material for a positive electrode material of a sodium ion battery, so as to inhibit the formation of a residual sodium phase on the surface of a positive electrode active material of the sodium ion battery, prevent electrolyte from corroding the positive electrode active material and enable the electrochemical performance of the sodium ion battery to be more stable.
In a first aspect of the present invention, there is provided a coating material for a positive electrode material of a sodium ion battery, the coating material comprising Na 6 Mg a Mn b N c (SO 4 ) 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a+b+c=1, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 0.2, and N is one or more than two of transition metal elements.
It is evident that the general formula Na 6 Mg a Mn b N c (SO 4 ) 4 Wherein the element N is not a transition metal element of Mg or Mn.
The N element is used as a doping element, the content is very small, and obviously a and b are not 0 at the same time.
When c is equal to 0, formula Na 6 Mg a Mn b N c (SO 4 ) 4 Can be expressed as Na 6 Mg a Mn b (SO 4 ) 4 Hereinafter, simply referred to as magnesium sodium manganese sulfate; when c is not equal to 0, formula Na 6 Mg a Mn b N c (SO 4 ) 4 The meaning is doped Na 6 Mg a Mn b (SO 4 ) 4 Hereinafter referred to as doped magnesium sodium manganese sulfate. In the invention, the magnesium sodium manganese sulfate is only represented by the general formula Na 6 Mg a Mn b (SO 4 ) 4 It is understood that the magnesium sodium manganese sulfate of the present invention may include a compound of the formula Na 6 Mg a Mn b (SO 4 ) 4 Middle a, etcIn the case where 0 or b is equal to 0.
In brief, the coating material provided by the invention comprises sodium magnesium sulfate and/or doped sodium magnesium sulfate, wherein the chemical formula of the sodium magnesium sulfate is Na 6 Mg a Mn b (SO 4 ) 4 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the main component of the coating material is sodium magnesium manganese sulfate and/or doped sodium magnesium manganese sulfate; more preferably, the coating material is sodium magnesium manganese sulfate and/or doped sodium magnesium manganese sulfate. When a=0, the above formula is Na 6 Mn(SO 4 ) 4 The method comprises the steps of carrying out a first treatment on the surface of the When b=0, the above formula is Na 6 Mg(SO 4 ) 4 。
Coating material Na 6 Mg a Mn b (SO 4 ) 4 Is P2 1 And/c, which belongs to simple monoclinic lattice crystals. Na (Na) 6 Mg(SO 4 ) 4 Is a=0.978 nm, b=0.920 nm, c=0.820 nm. The manganese (magnesium) oxygen octahedron and the sulfur-oxygen tetrahedron in the crystal are mutually connected into a three-dimensional structure, and the crystal has good structural stability.
Likewise, in the stabilized Na 6 Mg a Mn b (SO 4 ) 4 After a small amount of N element is doped in the structure, the obtained general formula is Na 6 Mg a Mn b N c (SO 4 ) 4 The substance of (C) can also maintain a stable crystal structure, and can be used as a coating material in a positive electrode material of a sodium ion battery.
In certain embodiments, the coating material of the present invention may also have the general formula Na 6 Me(SO 4 ) 4 Wherein Me represents a non-sodium metal element; me is generally a transition metal element. The molar ratio of Na to Me in the above formula is regarded as an important indicator of sodium content, and in existing similar sulphates, typically n (Na): n (Me). Ltoreq.1:1, e.g. Na 2 Fe 2 (SO 4 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the When n (Na): n (Me) > 2:1, it can be regarded as "high sodium". In the present invention, n (Na): n (Me) =6:1, so Na of the present invention 6 Me(SO 4 ) 4 Belonging to high sodium sulfate.
Due to Na 6 Me(SO 4 ) 4 The active material has homologous sodium ions with the positive electrode active material of the sodium ion battery, so that the enrichment of sodium ions in the active material to the surface of the active material can be prevented, the formation of a residual sodium phase on the surface of the active material can be inhibited, and the electrochemical performance of the sodium ion battery can be maintained. When such Na 6 Me(SO 4 ) 4 When the material is used as a coating material of a positive electrode material, the active material is Na 6 Me(SO 4 ) 4 A material-clad core material.
Because the magnesium sodium manganese sulfate has a very stable crystal structure, a small amount of doped magnesium sodium manganese sulfate also has a relatively stable structure, and therefore, the magnesium sodium manganese sulfate can be used as a coating material in the positive electrode material of the sodium ion battery.
In certain embodiments, doped magnesium sodium manganese sulfate refers to a small amount of doped transition metal element in place of manganese or magnesium element. The chemical general formula of the doped magnesium sodium manganese sulfate is Na 6 Mg a Mn b N c (SO 4 ) 4 Wherein c is more than 0 and less than or equal to 0.2, and the N element is at least one of iron, copper, zinc, chromium, nickel and cobalt; preferably, 0< c.ltoreq.0.1.
In some embodiments, small amounts of iron, copper, zinc, chromium, nickel, cobalt are used to dope instead of manganese or magnesium, without making large changes to the crystal structure, and still maintain the stability of the crystal structure.
Based on the above inventive concept, it is also conceivable for the person skilled in the art to dope other metal elements (such as alkali metal elements or monovalent metal elements) in sodium magnesium sulfate instead of a small amount of Na element; even small amounts of anions can be used instead of sulfate, the specific doping amounts being such that the stability of the sodium iron sulfate is not affected.
In certain embodiments, the particle size D50 of the coating material is 50-300nm, more preferably 60-200nm, such as 80-150nm.
In certain embodiments, the coating material has a specific surface area BET of 5 to 15m 2 /g。
In a second aspect of the present invention, a method for preparing a coating material for a positive electrode material of a sodium ion battery is provided, including:
taking sodium sulfate, manganese sulfate and/or magnesium sulfate as raw materials, sequentially dissolving the raw materials, evaporating to dryness, and grinding to obtain a coating material;
preferably, if it is desired to prepare doped sodium magnesium manganese sulfate, the feedstock also includes sulfates of doping elements (N elements), such as copper sulfate, zinc sulfate.
Preferably, the milling is performed by sanding to achieve a finer particle size of the coating material. The invention discovers that after the coating material reaches the nanometer level, the anode material can reach better electrochemical performance.
Preferably, the raw materials are soluble sulfates, and water is used for dissolving the raw materials.
Therefore, the preparation process of the coating material is simple, the coating material with stable space structure can be synthesized by adopting a wet synthesis route, and the coating material is easy to realize.
In certain embodiments, the method for preparing the coating material of the positive electrode material of the sodium ion battery comprises the following steps:
a dissolving step of dissolving sodium sulfate, and manganese sulfate and/or magnesium sulfate in a first solvent (the first solvent is preferably water) to obtain a first solution;
evaporating the first solvent in the first solution to obtain a solid substance;
grinding, namely mixing the solid substance with a second solvent to obtain a first mixture, and grinding the first mixture to obtain a first particle mixture;
and a drying step of drying the first particle mixture to obtain the coating material.
In the dissolving step of some embodiments, the ratio of the molar amounts of sodium sulfate, manganese sulfate, and magnesium sulfate is n (Na): n (Mn): n (Mg) =6:a:b, where a+b=1.
In the evaporating step of certain embodiments, heating in a water bath to maintain the temperature of the first solution at 50-80 ℃, and evaporating the first solvent in the first solution to obtain a solid substance;
in the milling step of some embodiments, the solid matter comprises 15% -30% of the solid content of the first mixture, the second solvent is preferably absolute ethanol, and the particle size of the first mixture of particles after milling is less than 200 nm;
in certain embodiments, the drying step is performed at a temperature of 40-60 ℃ for a time of 10-24 hours.
The invention provides a positive electrode material of a sodium ion battery, which has a core-shell structure and comprises a core and a coating layer coated on the surface of the core, wherein the coating layer comprises the coating material; preferably, the coating layer is composed of the coating material described above.
Preferably, the core is composed of a core material, the core material being a sodium ion layered oxide; typically, the layered oxide is a transition metal layered oxide, preferably the layered oxide is a P2 type or O3 type layered oxide.
Preferably, the core material has the chemical formula: na (Na) q (Ni x Mn y M z )O 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein 0.5<q≤1.05，0<x<1，0<y<1，0≤z<1, and x+y+z=1; m is at least one or more of Ti, fe, cu, li, co, mg, ca, sr, sn, zn, V, Y, la, ba, W, bi, al, ce, si. More preferably, 0<z<1。
Preferably, the coating comprises 0.05% to 5% by mass of the core, preferably 0.2% to 3%, more preferably 0.5% to 2%.
Preferably, the thickness of the coating layer is 50-500nm, preferably 60-200nm, more preferably 80-100nm.
The positive electrode material may include two or more coating layers. At this time, the coating layer formed by the coating material provided by the invention is preferably positioned on the outermost layer of the positive electrode material, so that the electrolyte can be prevented from corroding the inside of the positive electrode material to the greatest extent.
In some embodiments, the ratio of the thickness of the coating layer to the particle size of the positive electrode material is 1:5-100, and may be 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, and ranges between the above ratios. The thickness of the coating is not a fixed value and can be represented by measuring several (e.g. 5) values and averaging them. If 5 values are taken, the measurement can be carried out once every 72 DEG; similarly, if 6, 9, 10, 12 values are taken, the measurement is performed at intervals of 60 °, 40 °, 36 °, 30 °. Regardless of the manner of measurement, the coating layer has a small thickness ratio compared to the granularity of the positive electrode material.
In certain embodiments, the coating material has a specific surface area BET of 5 to 15m 2 And/g, the particle size D50 is 50-300nm. In certain embodiments, after being prepared into a positive electrode material for a sodium ion battery, the positive electrode material has a specific surface area BET of 0.25 to 2m 2 Per gram, a compaction density of 2.4-3.3g/cm 3 The particle size D50 is 5-20 microns.
In certain embodiments, the particle size D50 of the positive electrode material is preferably 10-15 microns.
According to a fourth aspect of the present invention, there is provided a method for preparing the positive electrode material of a sodium ion battery, the method comprising:
and (3) obtaining a coating material, mixing the coating material with the core material, and then annealing and crushing to obtain the anode material. It can be seen that the present invention separately obtains the prepared clad material and core material, and mixes them. When mixed, the coating material accounts for 0.05-5% of the mass of the core material, preferably 0.2-3%, and more preferably 0.5-2%. Preferably, the annealing is performed in an oxygen-containing atmosphere at a temperature of 200-400 ℃ for a time of 3-6 hours.
Preferably, mixing comprises dry mixing or wet mixing; the dry mixing is to directly mix the cladding material and the core material; the wet mixing is to disperse the coating material in the solvent, then add the kernel material into the solvent, and mix; wherein the coating material is insoluble or slightly soluble in the solvent; preferably, the solvent is an alcoholic solvent; more preferably, the solvent is absolute ethanol.
In some embodiments of the present invention, the preparation method of the positive electrode material of the sodium ion battery may be divided into: the preparation step, the coating step and the pulverizing step, wherein the coating step can be divided into a mixing step and an annealing step. The mixing step is to mix the cladding material with the core material, and the annealing step is to heat treat the mixed material.
In certain embodiments, the core material is prepared by mixing and sintering a sodium source (including at least one or more of sodium carbonate, sodium hydroxide, or sodium nitrate) and a precursor in a molar amount ratio of (0.5-1.05): 1. In certain embodiments, the coating material is prepared as described above.
In some embodiments, the coating material is mixed with the core material to provide a coated second mixture. Preferably, the mixing step comprises dry mixing or wet mixing: wherein, dry mixing, the coating material is directly mixed with the core material to obtain a coated second mixture; wet mixing, dissolving the coating material in a third solvent which is preferably absolute ethyl alcohol, adding the core material into the third solvent, and coating to obtain a coated second mixture.
In the annealing step of certain embodiments, the second mixture is annealed under oxygen-containing atmosphere conditions and cooled to room temperature. Preferably, in the annealing step, the annealing temperature is 200-400 ℃ and the annealing time is 3-6h.
In some embodiments, the second mixture after cooling is crushed to obtain a sodium ion battery cathode material.
In summary, the coating material of the sodium ion battery anode material, the anode material and the preparation method thereof provided by the invention have at least the following beneficial effects:
the coating material disclosed by the invention has stable properties, and when the coating material is used for coating the core material, a protective layer can be formed on the surface of the core material, so that the core material is prevented from being directly contacted with electrolyte, the corrosion of the electrolyte to the positive electrode material is slowed down, the occurrence of side reaction is reduced, and the cycle performance is improved. The coating material provided by the invention has a stable space structure and is prepared in Na + The structure of the positive electrode material can be stabilized in the deintercalation process, so that the collapse of the structure is prevented, and the circulation stability is improved.
The coating material disclosed by the invention is high-sodium sulfate, and when the coating material is used for coating the core material, a high-sodium phase can be formed on the surface of the core material, so that the enrichment of sodium ions in the core material on the surface is reduced, the formation of residual sodium phases on the surface of the core material is inhibited, and the circulation stability is improved.
The preparation process of the coating material and the anode material disclosed by the invention is simple, and the coating material is coated on the surface of the core material after being prepared, so that the coating material and the anode material can be suitable for surface coating of different types of core materials.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are some embodiments of the invention and that other drawings can be obtained from them without inventive effort for a person skilled in the art.
Fig. 1: 0.1C charge-discharge performance graphs of example 1 and comparative example 1;
fig. 2: a 50-turn 1C cycle retention plot for example 1 and comparative example 1;
fig. 3: nanoscale Na prepared in example 1 6 Mn(SO 4 ) 4 An XRD pattern of (b);
fig. 4: nanoscale Na prepared in example 1 6 Mn(SO 4 ) 4 XRD pattern after calcination at 500 ℃ for 4h;
fig. 5: nanoscale Na prepared in example 4 6 Mg(SO 4 ) 4 An XRD pattern of (b);
fig. 6: nanoscale Na prepared in example 4 6 Mg(SO 4 ) 4 XRD pattern calcined at 500 ℃ for 20 h;
fig. 7: nanoscale Na prepared in example 1 6 Mn(SO 4 ) 4 SEM images of (a);
fig. 8: SEM image of the positive electrode material prepared in example 1;
fig. 9: XRD pattern of the positive electrode material prepared in example 1;
fig. 10: CP diagram of the positive electrode material prepared in example 1;
fig. 11: an EDS plot of the S content of the positive electrode material prepared in example 1;
fig. 12: SEM image of the uncoated positive electrode material prepared in comparative example 1 at 5000 magnification;
fig. 13: SEM image of the uncoated positive electrode material prepared in comparative example 1 at 50000 magnification;
fig. 14: XRD pattern of the uncoated positive electrode material prepared in comparative example 1.
Detailed Description
To further clarify the above and other features and advantages of the present invention, a further description of the invention will be rendered by reference to the appended drawings. It should be understood that the specific embodiments described herein are for illustrative purposes only and are not limiting, as to those skilled in the art.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the specific details need not be employed to practice the present invention. In other instances, well-known steps or operations have not been described in detail in order to avoid obscuring the invention.
The particle size and the particle diameter in the present invention are all D50 values, and the content and the percentage of the coating amount are all mass percentages unless otherwise specified.
The chemical properties of the magnesium sodium manganese sulfate and/or the doped magnesium sodium manganese sulfate coating material disclosed by the invention are stable, and the coating material can still be kept stable after calcination at 500 ℃. Therefore, by coating the surface of the core material with a layer of coating material with stable properties, the direct contact between the core material and the electrolyte can be avoided, the erosion of the electrolyte to the core material is relieved, the structural stability of the core material is improved, and the cycle performance of the core material is improved.
In addition, in the coating material disclosed by the invention, n (Na): n (Me) =6:1, wherein Me is a metal element except Na in the coating material, and belongs to high sodium sulfate (high sodium definition: n (Na): n (Me) > 2:1), and because the coating material has homologous sodium ions with a sodium ion battery, the enrichment of sodium ions in the core material to the surface of the core material can be prevented, the formation of a residual sodium phase on the surface of the core material is inhibited, the electrochemical performance of the sodium ion battery is maintained, and the cycling stability is improved.
In some embodiments, the spatial group of the coating material is P2 1 C, belonging to simple monoclinic lattice crystals; na (Na) 6 Mg(SO 4 ) 4 Is a=0.978 nm, b=0.920 nm, c=0.820 nm. The manganese (magnesium) oxygen octahedron and the sulfur oxygen tetrahedron in the crystal are mutually connected into a three-dimensional structure, and have good structural stability, namely, in Na + The crystal structure can be maintained stable in the process of deintercalation, the collapse of the crystal structure is prevented, and the circulation stability is improved.
In some embodiments, the method of making the coating material includes:
a dissolution step of weighing an appropriate amount of Na in such a way that n (Na): n (Mn): n (Mg) =6:a:b (a+b=1) 2 SO 4 、MnSO 4 、MgSO 4 Adding 1L of deionized water into a container, and continuously stirring at a speed of 100-1000rpm until solid substances are completely dissolved to obtain a mixed solution;
evaporating, namely continuously stirring the mixed solution for 10-24 hours at the speed of 100-1000rpm under the water bath heating condition of 50-80 ℃ until the water is evaporated to obtain a solid substance;
grinding, further mixing the solid substance with absolute ethyl alcohol according to the solid content of 15% -30%, and then crushing the mixture for 2-6 hours by adopting a sand mill;
drying, namely drying the sanded mixture in a vacuum drying oven at a low temperature of 40-60 ℃ for 10-24 hours to obtain a coating material Na 6 Mg a Mn b (SO 4 ) 4 。
Wherein in the dissolving step and the evaporating step, the liquid is continuously stirred at a speed of 100-1000rpm, and the liquid is heated in water bath to maintain the temperature of 50-80 ℃ so as to enable Na 2 SO 4 With MnSO 4 And/or MgSO 4 Can react fully.
The solid substance and the absolute ethyl alcohol are mixed according to the solid content of 15-30 percent so as to grind the coating material into nano materials, the nano materials are more uniform when the inner core material is coated, and the particle size after grinding is required to be below 200nm so as to coat the inner core material.
Drying under vacuum at low temperature (40-60deg.C) to avoid agglomeration of the nanomaterial.
In some embodiments, a method of preparing a positive electrode material includes:
uniformly mixing a sodium source (sodium carbonate, sodium hydroxide, sodium nitrate and the like) and a precursor according to a molar ratio of 0.5-1.05:1, calcining for 10-15h at 650-1000 ℃ under the condition of oxygen-containing atmosphere, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
mixing step, the prepared coating material Na 6 Mg a Mn b (SO 4 ) 4 Mixing and coating the material with the core material according to the coating amount of 0.05% -5%;
wherein, the cladding amount refers to: the coating material comprises the mass fraction of the core material. The mixing step may employ dry mixing or wet mixing. Dry mixing: the core material and the coating material Na 6 Mg a Mn b (SO 4 ) 4 Weighing according to the coating amount, and stirring and mixing in a stirrer at a speed of 2000-3000rpm for 2min. Wet mixing the core material with the coating material Na 6 Mg a Mn b (SO 4 ) 4 Weighing according to coating amount, and coating material Na 6 Mg a Mn b (SO 4 ) 4 Placing into a container containing absolute ethyl alcohol, and oscillating for 20min by using an ultrasonic cleaner to fully disperse the ultrasonic cleaner in the absolute ethyl alcohol. The core material was added thereto while stirring for 10-20min using a glass rod to be thick paste.
Annealing, namely annealing the mixture for 3-6 hours at 200-400 ℃ under the condition of oxygen-containing atmosphere, and naturally cooling to room temperature; wherein, the low temperature annealing is carried out at 200-400 ℃ to carry out low temperature coating, and meanwhile, the high temperature decomposition of the coating material is avoided.
Crushing, namely crushing the cooled mixture, and sieving the crushed mixture by adopting a 400-mesh screen to obtain the coated sodium ion battery anode material.
The invention relates to a method for preparing a sodium ion battery based on a sodium ion battery anode material, which comprises the following steps: the positive electrode material of the prepared sodium ion battery, the conductive agent and the adhesive are uniformly stirred in NMP solvent (N-methyl pyrrolidone), and then coated on aluminum foil. And then baking, rolling and slicing are carried out to prepare the positive pole piece. And assembling the positive electrode plate, the diaphragm, the sodium plate, the gasket and the like to form the sodium ion button cell.
The invention adopts a battery test cabinet to test the manufactured sodium ion button battery, and the test conditions of the embodiment 5 and the comparative example 3 are as follows: the sodium sheet is used as a negative electrode, activated under the condition of 0.1C, and subjected to a cyclic test (1 C=130 mA/g) under the condition of 1℃, wherein the voltage range is 2.0-4.0V, and the test temperature is 25+/-1 ℃. The test conditions for the remaining examples and comparative examples were: the sodium sheet is used as a negative electrode, activated under the condition of 0.1C, and subjected to a cyclic test (1 C=150 mA/g) under the condition of 1℃, wherein the voltage range is 2.0-4.2V, and the test temperature is 25+/-1 ℃.
The following further illustrates the advantages of the solution provided by the present invention with the detection results of the specific examples.
Example 1
Nanometer Na 6 Mn(SO 4 ) 4 Is prepared from the following steps:
(1) Weighing a proper amount of Na according to the ratio of n (Na): n (Mn) =6:1 2 SO 4 、MnSO 4 Adding 1L of deionized water into a container, and continuously stirring at a speed of 500rpm until the deionized water is completely dissolved to obtain a mixed solution;
(2) Continuously stirring the mixed solution for 12 hours at the speed of 500rpm under the water bath heating condition of 60 ℃ until the water is evaporated to dryness to obtain a solid substance;
(3) Further mixing the solid substance with absolute ethyl alcohol according to the solid content of 15%, and then crushing the mixture for 3 hours by adopting a sand mill;
(4) Drying the sanded mixture in a vacuum drying oven at 40 ℃ for 12 hours to obtain a coating material Na 6 Mn(SO 4 ) 4 。
Preparing a positive electrode material:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 Uniformly mixing according to the mole ratio of Na element to precursor of 1.01:1, and thenCalcining for 12 hours at 850 ℃ under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
(2) Coating material Na prepared by the method 6 Mn(SO 4 ) 4 Fully mixing the material with the core material according to the coating amount of 1%;
(3) Annealing the mixture for 4 hours at 300 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(4) Crushing the cooled mixture, and sieving the crushed mixture by a 400-mesh screen to obtain the positive electrode material of the sodium ion battery.
(5) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the initial charge capacity of 0.1C is 183.3mAh/g, the initial discharge capacity of 0.1C is 165.8mAh/g, and the 1C cycle retention rate is 87.8%.
Example 2:
nanometer Na 6 Mn(SO 4 ) 4 Preparation of (C) as in example 1
Preparing a positive electrode material:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.03:1, calcining at 880 ℃ for 12 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
(2) Coating material Na prepared by the method 6 Mn(SO 4 ) 4 Fully mixing the modified starch with the core material according to the coating amount of 1.5%;
(3) Annealing the mixture for 5 hours at 350 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(4) Crushing the cooled mixture, and sieving the crushed mixture by a 400-mesh screen to obtain the positive electrode material of the sodium ion battery.
(5) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the initial charge capacity of 0.1C is 179.3mAh/g, the initial discharge capacity of 0.1C is 166.2mAh/g, and the 1C cycle retention rate is 87.3%.
Example 3:
nanometer Na 6 Mn(SO 4 ) 4 Preparation of (C) as in example 1
Preparing a positive electrode material:
(1) Sodium hydroxide and precursor Ni 0.6 Mn 0.2 Fe 0.2 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.05:1, calcining at 700 ℃ for 12 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
(2) Coating material Na prepared by the method 6 Mn(SO 4 ) 4 Fully mixing the material with the core material according to the coating amount of 2%;
(3) Annealing the mixture for 4 hours at 400 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(4) Crushing the cooled mixture, and sieving the crushed mixture by a 400-mesh screen to obtain the positive electrode material of the sodium ion battery.
(5) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the first charge capacity of 0.1C is 192.5mAh/g, the first discharge capacity of 0.1C is 178.9mAh/g, and the 1C cycle retention rate is 80.5%.
Example 4:
nanometer Na 6 Mg(SO 4 ) 4 Is prepared from the following steps:
(1) Weighing a proper amount of Na according to the ratio of n (Na): n (Mg) =6:1 2 SO 4 、MgSO 4 Adding 1L of deionized water into a container, and continuously stirring at a speed of 800rpm until the deionized water is completely dissolved to obtain a mixed solution;
(2) Continuously stirring the mixed solution for 12 hours at the speed of 800rpm under the water bath heating condition of 50 ℃ until the water is evaporated to dryness to obtain a solid substance;
(3) Further mixing the solid substance with absolute ethyl alcohol according to the solid content of 20%, and then crushing the mixture for 4 hours by adopting a sand mill;
(4) The sanded mixture is arranged inDrying in a vacuum drying oven at 50 ℃ for 12 hours to obtain the coating material Na 6 Mg(SO 4 ) 4 。
Preparing a positive electrode material:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.02:1, calcining at 800 ℃ for 12 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
(2) Coating material Na prepared by the method 6 Mg(SO 4 ) 4 Fully mixing the material with the core material according to the coating amount of 0.5%;
(3) Annealing the mixture for 5 hours at 250 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(4) Crushing the cooled mixture, and sieving the crushed mixture by a 400-mesh screen to obtain the positive electrode material of the sodium ion battery.
(5) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the initial charge capacity of 0.1C is 179.1mAh/g, the initial discharge capacity of 0.1C is 164.7mAh/g, and the 1C cycle retention rate is 86.8%.
Example 5:
nanometer Na 6 Mn 0.8 Mg 0.2 (SO 4 ) 4 Is prepared from the following steps:
(1) Weighing proper amount of Na according to the ratio of n (Na) to n (Mn) to n (Mg) =6:0.8:0.2 2 SO 4 、MgSO 4 、MgSO 4 Adding 1L of deionized water into a container, and continuously stirring at a speed of 1000rpm until the deionized water is completely dissolved to obtain a mixed solution;
(2) Continuously stirring the mixed solution for 15 hours at the speed of 1000rpm under the water bath heating condition of 60 ℃ until the water is evaporated to dryness to obtain a solid substance;
(3) Further mixing the solid substance with absolute ethyl alcohol according to the solid content of 25%, and then crushing the mixture for 6 hours by adopting a sand mill;
(4) Placing the sanded mixture in a vacuum drying ovenDrying at 45 ℃ for 15 hours to obtain the coating material Na 6 Mn 0.8 Mg 0.2 (SO 4 ) 4 。
Preparing a positive electrode material:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.67 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 0.67:1, calcining at 950 ℃ for 15 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
(2) Coating material Na prepared by the method 6 Mn 0.8 Mg 0.2 (SO 4 ) 4 Fully mixing the material with the core material according to the coating amount of 1%;
(3) Annealing the mixture for 6 hours at 350 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(4) Crushing the cooled mixture, and sieving the crushed mixture by a 400-mesh screen to obtain the positive electrode material of the sodium ion battery.
(5) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the first charge capacity of 0.1C is 93.9mAh/g, the first discharge capacity of 0.1C is 86.9mAh/g, and the 1C cycle retention rate is 97.8%.
Example 6:
nanometer Na 6 Mn 0.5 Mg 0.5 (SO 4 ) 4 Is prepared from the following steps:
(1) Weighing proper amount of Na according to the ratio of n (Na) to n (Mn) to n (Mg) =6:0.5:0.5 2 SO 4 、MgSO 4 、MgSO 4 Adding 1L of deionized water into a container, and continuously stirring at a speed of 1000rpm until the deionized water is completely dissolved to obtain a mixed solution;
(2) Continuously stirring the mixed solution for 15 hours at the speed of 1000rpm under the water bath heating condition of 60 ℃ until the water is evaporated to dryness to obtain a solid substance;
(3) Further mixing the solid substance with absolute ethyl alcohol according to the solid content of 25%, and then crushing the mixture for 6 hours by adopting a sand mill;
(4) Mixing the sand ground materialsThe compound is dried for 12 hours in a vacuum drying oven at 50 ℃ to obtain the coating material Na 6 Mn 0.5 Mg 0.5 (SO 4 ) 4 。
Preparing a positive electrode material:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.03:1, calcining at 950 ℃ for 15 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
(2) Coating material Na prepared by the method 6 Mn 0.5 Mg 0.5 (SO 4 ) 4 Fully mixing the material with the core material according to the coating amount of 1%;
(3) Annealing the mixture for 5 hours at 400 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(4) Crushing the cooled mixture, and sieving the crushed mixture by a 400-mesh screen to obtain the positive electrode material of the sodium ion battery.
(5) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the first charge capacity of 0.1C is 182.1mAh/g, the first discharge capacity of 0.1C is 164.5mAh/g, and the 1C cycle retention rate is 87.9%.
Example 7:
nanometer Na 6 Mn 0.2 Mg 0.8 (SO 4 ) 4 Is prepared from the following steps:
(1) Weighing proper amount of Na according to the ratio of n (Na) to n (Mn) to n (Mg) =6:0.2:0.8 2 SO 4 、MgSO 4 、MgSO 4 Adding 1L of deionized water into a container, and continuously stirring at a speed of 1000rpm until the deionized water is completely dissolved to obtain a mixed solution;
(2) Continuously stirring the mixed solution for 15 hours at the speed of 1000rpm under the water bath heating condition of 60 ℃ until the water is evaporated to dryness to obtain a solid substance;
(3) Further mixing the solid substance with absolute ethyl alcohol according to the solid content of 25%, and then crushing the mixture for 6 hours by adopting a sand mill;
(4) Drying the sanded mixture in a vacuum drying oven at 45 ℃ for 15 hours to obtain a coating material Na 6 Mn 0.2 Mg 0.8 (SO 4 ) 4 。
Preparing a positive electrode material:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.02:1, calcining at 950 ℃ for 15 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain a core material;
(2) 1.5g of the coating material Na prepared above was reacted 6 Mn 0.2 Mg 0.8 (SO 4 ) 4 Adding into a container containing 50ml of absolute ethyl alcohol, placing the container into an ultrasonic cleaner, performing ultrasonic vibration for 20min, adding 100g of core material into the container, stirring for 10min by using a glass rod to enable the anode material to be thick paste, and fully mixing the core material and the coating material;
(3) Annealing the mixture for 5 hours at 350 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(4) Crushing the cooled mixture, and sieving the crushed mixture by a 400-mesh screen to obtain the positive electrode material of the sodium ion battery.
(5) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the primary charge capacity of 0.1C is 181.7mAh/g, the primary discharge capacity of 0.1C is 164.3mAh/g, and the 1C cycle retention rate is 88.1%.
Comparative example 1:
Na(Ni 0.33 Mn 0.33 Fe 0.34 )O 2 preparation:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.01:1, calcining at 850 ℃ for 12 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain Na (Ni) 0.33 Mn 0.33 Fe 0.34 )O 2 ；
(2) Annealing the prepared core material for 4 hours at 300 ℃ under the air atmosphere condition, naturally cooling to room temperature, crushing, and sieving with 400 meshes to obtain an uncoated Na (Ni0.33Mn0.33Fe0.34) O2 anode material after annealing;
(3) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the first charge capacity of 0.1C is 175.9mAh/g, the first discharge capacity of 0.1C is 158.8mAh/g, and the 1C cycle retention rate is 81.1%.
Comparative example 2:
Na(Ni 0.6 Mn 0.2 Fe 0.2 )O 2 preparation:
(1) Sodium hydroxide and precursor Ni 0.6 Mn 0.2 Fe 0.2 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.05:1, calcining at 700 ℃ for 12 hours under the condition of oxygen atmosphere, cooling to room temperature, crushing, and sieving with 400 meshes to obtain Na (Ni) 0.6 Mn 0.2 Fe 0.2 )O 2 ；
(2) Annealing the prepared core material for 4 hours at 400 ℃ under the air atmosphere condition, naturally cooling to room temperature, crushing, sieving with 400 meshes to obtain uncoated Na (Ni) after annealing 0.6 Mn 0.2 Fe 0.2 )O 2 And a positive electrode material.
(3) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the first charge capacity of 0.1C is 197.1mAh/g, the first discharge capacity of 0.1C is 185.1mAh/g, and the 1C cycle retention rate is 72.1%.
Comparative example 3:
Na 0.67 (Ni 0.33 Mn 0.67 )O 2 preparation
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.67 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 0.67:1, calcining at 950 ℃ for 12 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain Na 0.67 (Ni 0.33 Mn 0.67 )O 2 ；
(2) Annealing the prepared material under the condition of air atmosphere at 350 ℃ for 6 hours, naturally cooling to room temperature, crushing and sieving with 400 meshes to obtain the uncoated Na after annealing 0.67 (Ni 0.33 Mn 0.67 )O 2 And a positive electrode material.
(3) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the first charge capacity of 0.1C is 96.5mAh/g, the first discharge capacity of 0.1C is 87.2mAh/g, and the 1C cycle retention rate is 94.5%.
Comparative example 4:
(1) Sodium carbonate and precursor Ni 0.33 Mn 0.33 Fe 0.34 (OH) 2 Uniformly mixing according to the molar ratio of Na element to precursor of 1.01:1, calcining at 850 ℃ for 12 hours under the air atmosphere condition, cooling to room temperature, crushing, and sieving with 400 meshes to obtain the core material Na (Ni) 0.33 Mn 0.33 Fe 0.34 )O 2 ；
(2) Na is mixed with 2 SO 4 、MnSO 4 、MgSO 4 Mixing according to the ratio of n (Na): n (Mn): n (Mg) =6:0.5:0.5 to obtain a mixture;
(3) Mixing the above mixture with (1) a core material Na (Ni) 0.33 Mn 0.33 Fe 0.34 )O 2 Fully mixing according to the coating amount of 3%;
(4) Annealing the mixture for 5 hours at 400 ℃ under the air atmosphere condition, and naturally cooling to room temperature;
(5) Crushing the cooled mixture, and sieving the crushed mixture by adopting a 400-mesh screen to obtain the anode material.
(6) And assembling the prepared positive electrode material and a sodium sheet into a button cell for testing.
Detection result: the primary charge capacity of 0.1C is 165.1mAh/g, the primary discharge capacity of 0.1C is 160.6mAh/g, and the 1C cycle retention rate is 71.6%.
Table-electrochemical performance table for each example and comparative example
In the following description with reference to table 1 and fig. 1 to 14, examples 1, 2, 4, 6 and 7 are compared with comparative example 1 (see fig. 5 and 6), example 3 is compared with comparative example 2, and example 5 is compared with comparative example 3, and when the core material or the cathode material is the same, the cycle performance of the cathode material after the core material is coated with the coating material provided by the present invention is significantly better than that of the cathode material not coated in comparative example 1 to 3, and surprisingly, the ternary cathode material in some examples is also partially improved in capacity due to coating.
Referring to FIGS. 3-6, na in example 1 can be seen 6 Mn(SO 4 ) 4 And Na in example 4 6 Mg(SO 4 ) 4 XRD patterns after calcination at 500℃were unchanged, indicating Na 6 Mn(SO 4 ) 4 And Na (Na) 6 Mg(SO 4 ) 4 Is stable in properties, i.e. the coating material Na disclosed in the invention 6 Mg a Mn b (SO 4 ) 4 The property of the polymer is stable, and when the polymer is used as a coating material of a positive electrode material, electrolyte can be prevented from corroding a core material, and side reactions are reduced.
Referring to fig. 7, it can be seen that the particle size of the coating material prepared in example 1 was around 100nm. Comparing fig. 8 with fig. 12, it can be seen that the surface morphology of the positive electrode material is significantly different, comparing fig. 9 with fig. 14, it can be seen that the XRD information of the positive electrode material is also significantly different, further referring to fig. 10, the surface of the core material in example 1 has a uniform nano coating layer. The element distribution analysis of the coating material shows that the content of the S element at the nano coating layer on the surface of the cathode material is obviously increased from fig. 11, which shows that the coating is successful, that is, the coating material with high concentration of Na on the surface of the core material in example 1 is located on the surface of the core. While referring to fig. 13, the surface of the positive electrode material of comparative example 1 has protrusions densely and unevenly distributed, presumably high concentration of Na, because Na in the positive electrode material of comparative example 1 is enriched toward the surface thereof, forming a sodium residue phase, resulting in a decrease in electrochemical performance of the positive electrode material of comparative example 1. The coating material provided by the invention is used for coating the core material, so that the formation of the residual sodium phase on the surface of the positive electrode material can be inhibited, and the electrochemical performance of the core material is kept stable.
In addition, referring to table one, it can be seen that in comparative example 4, since the core material is coated with the raw material for preparing the coating material, the electrochemical performance of the core material is improved much less than that of the coating material of example 6, as compared with comparative example 4. Therefore, the raw materials for preparing the coating material provided by the invention are used for coating the core material, so that the effect of coating the core material cannot be achieved, and the electrochemical performance of the core material cannot be maintained.
The technical features described above may be arbitrarily combined. Although not all possible combinations of features are described, any combination of features should be considered to be covered by the description provided that such combinations are not inconsistent.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A coating material of a positive electrode material of a sodium ion battery is characterized by comprising Na 6 Mg a Mn b N c (SO 4 ) 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein a+b+c=1, a is more than or equal to 0 and less than or equal to 1, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 0.2, and N is one or more than two of transition metal elements.
2. The coating material of the positive electrode material of the sodium ion battery according to claim 1, wherein the N element is at least one of iron, copper, zinc, chromium, nickel, and cobalt;
and/or, c is more than or equal to 0 and less than or equal to 0.1;
and/or the particle size D50 of the coating material is 50-300nm;
and/or the specific surface area BET of the coating material is 5-15m 2 /g。
3. A method for preparing a coating material of a positive electrode material of a sodium ion battery according to claim 1 or 2, wherein,
taking sodium sulfate, manganese sulfate and/or magnesium sulfate as raw materials, sequentially dissolving, evaporating to dryness and grinding the raw materials to obtain the coating material;
preferably, the raw material further comprises sulfate of the N element;
preferably, the milling is performed by sanding;
preferably, the drying is carried out after grinding;
preferably, the raw materials are soluble sulfates, and water is used for dissolving the raw materials.
4. A positive electrode material of a sodium ion battery, which is characterized by having a core-shell structure and comprising an inner core and a coating layer coated on the surface of the inner core, wherein the coating layer comprises the coating material of claim 1 or 2;
preferably, the coating layer is composed of the coating material according to claim 1 or 2.
5. The positive electrode material of a sodium ion battery according to claim 4, wherein the core is composed of a core material, the core material being a sodium ion layered oxide;
preferably, the sodium ion layered oxide is a P2 type or O3 type sodium ion layered oxide.
6. According toThe positive electrode material of a sodium ion battery of claim 4, wherein the core is comprised of a core material having the chemical formula: na (Na) q (Ni x Mn y M z )O 2 ；
Wherein 0.5< q.ltoreq.1.05, 0< x <1,0< y <1, 0.ltoreq.z <1, and x+y+z=1;
m is at least one or more of Ti, fe, cu, li, co, mg, ca, sr, sn, zn, V, Y, la, ba, W, bi, al, ce, si.
7. The positive electrode material for a sodium ion battery according to any one of claim 4 to 6, wherein,
the coating layer accounts for 0.05-5% of the mass of the inner core, preferably 0.2-3%, and more preferably 0.5-2%.
8. The positive electrode material for a sodium ion battery according to any one of claim 4 to 6, wherein,
the coating layer is positioned on the outermost layer of the positive electrode material;
and/or the particle size D50 of the positive electrode material is 5-20 micrometers;
and/or the specific surface area BET of the positive electrode material is 0.25-2m 2 /g；
And/or the positive electrode material has a compacted density of 2.4-3.3g/cm 3 ；
And/or the thickness of the coating layer is 50-500nm, preferably 60-200nm, more preferably 80-100nm;
and/or the ratio of the thickness of the coating layer to the granularity of the positive electrode material is 1:5-100.
9. A method for preparing the positive electrode material of the sodium ion battery as claimed in any one of claims 4 to 8, comprising:
the coating material is obtained, and after the coating material is mixed with the core material, annealing and crushing are carried out to obtain the anode material;
preferably, the coating material comprises 0.05% -5% by mass of the core material, preferably 0.2% -3%, more preferably 0.5% -2% by mass of the core material when mixed;
preferably, the annealing is performed in an oxygen-containing atmosphere, the annealing temperature is 200-400 ℃, and the annealing time is 3-6h.
10. The method for preparing a positive electrode material of a sodium ion battery according to claim 9, wherein the mixing comprises dry mixing or wet mixing;
the dry mixing is to directly mix the cladding material with the core material; the wet mixing is to disperse the coating material in a solvent, then add the core material into the solvent, and mix;
wherein the coating material is insoluble or slightly soluble in the solvent; preferably, the solvent is an alcoholic solvent; more preferably, the solvent is absolute ethanol.
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