CN116924488B - Precursor of sodium ion battery anode material, preparation method and application thereof - Google Patents
Precursor of sodium ion battery anode material, preparation method and application thereof Download PDFInfo
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- CN116924488B CN116924488B CN202311198862.5A CN202311198862A CN116924488B CN 116924488 B CN116924488 B CN 116924488B CN 202311198862 A CN202311198862 A CN 202311198862A CN 116924488 B CN116924488 B CN 116924488B
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- precursor
- ion battery
- sodium ion
- positive electrode
- electrode material
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- 239000002243 precursor Substances 0.000 title claims abstract description 53
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000010405 anode material Substances 0.000 title description 14
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000007774 positive electrode material Substances 0.000 claims abstract description 31
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical group [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims abstract description 29
- 239000005750 Copper hydroxide Substances 0.000 claims abstract description 27
- 229910001956 copper hydroxide Inorganic materials 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 80
- 239000013078 crystal Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 238000000975 co-precipitation Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 239000000787 lecithin Substances 0.000 claims description 3
- 229940067606 lecithin Drugs 0.000 claims description 3
- 235000010445 lecithin Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 229960004274 stearic acid Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 81
- 239000008139 complexing agent Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 12
- 238000007873 sieving Methods 0.000 description 12
- 239000012716 precipitator Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- CDUFCUKTJFSWPL-UHFFFAOYSA-L manganese(II) sulfate tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O CDUFCUKTJFSWPL-UHFFFAOYSA-L 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000003892 spreading Methods 0.000 description 6
- 230000007480 spreading Effects 0.000 description 6
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- -1 heptahydrate ferrous sulfate Chemical class 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
-
- 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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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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
- C01P2004/01—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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
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- 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
-
- 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
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the technical field of sodium ion battery materials, and discloses a precursor of a sodium ion battery positive electrode material, wherein the precursor is in a core-shell structure, a core is copper hydroxide, and a shell is a binary, ternary or multi-element precursor material. The positive electrode material is obtained by sintering the precursor, and has a hollow structure, so that the stress caused by the change of the volume of the material in the charge and discharge process of the battery can be relieved, and better cycle stability is provided. In addition, cu in the positive electrode material 2+ Compared with Ni 2+ The air stability of the material is increased while providing charge compensation, effectively improving the electrochemical performance of the material and reducing the material cost.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a sodium ion battery positive electrode material, a precursor thereof and a preparation method thereof.
Background
Sodium and lithium belong to the same main group, and many physicochemical properties are similar, so that the possibility of research and development of sodium ion batteries is determined. Compared with a lithium ion battery, a sodium ion battery has two advantages: firstly, the raw material cost is low, high-valence rare metals such as lithium, cobalt and the like are not used, and the greatest advantage of sodium is that the sodium is rich in resources such as seawater and the like and is an inexhaustible element; secondly, the existing production process can be used, the working mechanism of the sodium ion battery is the same as that of the lithium battery, and the existing production equipment of battery enterprises can be directly used for producing the sodium ion battery, so that the enterprises can easily take the sodium ion battery as a substitute battery for production because equipment investment is not basically needed.
The sodium ion battery anode material is one of important factors influencing parameters such as battery energy density, cycle performance, rate performance and the like, and researchers always consider the research of the sodium ion battery anode material very important.
Disclosure of Invention
It is an object of the present invention to provide a precursor for a positive electrode material of a sodium ion battery.
The second object of the invention is to provide a preparation method of the precursor of the positive electrode material of the sodium ion battery.
The invention further provides a positive electrode material of the sodium ion battery.
The fourth object of the invention is to provide a sodium ion battery.
In order to achieve the above object, the present invention provides the following specific technical solutions.
Firstly, the invention provides a precursor of a positive electrode material of a sodium ion battery, wherein the precursor has a core-shell structure, a core is copper hydroxide, and a shell is a binary, ternary or multi-element precursor material.
In a further preferred embodiment, the particle diameter of the core is 1 to 10 μm, and the particle diameter of the precursor is 5 to 15 μm.
In a further preferred embodiment, the binary, ternary or multi-element precursor material has the chemical formula Ni x1 Mg x2 Fe y Mn z1 Ti z2 (OH) 2 Wherein 0.ltoreq.x1.ltoreq.0.5, 0.ltoreq.x2.ltoreq.0.1, 0.3.ltoreq.y 0.7,0.3.ltoreq.z1.ltoreq. 0.7,0.ltoreq.z2.ltoreq.0.1, x1+x2+y+z1+z2=1.
Secondly, the invention provides a preparation method of the precursor of the sodium ion battery anode material, which comprises the following steps:
step S1, preparing copper salt solution; slowly adding the precipitant into a reaction kettle containing copper salt solution and a soft template for reaction, filtering and washing to obtain copper hydroxide seed crystals;
s2, depositing binary, ternary or multi-element precursor materials on the surface of the seed crystal by a coprecipitation method;
and S3, filtering the slurry, washing and drying the solid phase to obtain a precursor.
In a further preferred embodiment, the copper salt is at least one of copper sulfate, copper nitrate, and copper chloride; the concentration of the copper salt solution is 0.5-5.0 mol/L.
In a further preferred embodiment, the precipitant is at least one of ammonia water, sodium hydroxide, and potassium hydroxide.
In a further preferred embodiment, the soft template is at least one of polyethylene glycol 400, lecithin, and stearic acid.
In a further preferred embodiment, the temperature of the reaction in step S1 is 50 to 70 ℃.
In addition, the invention provides a positive electrode material of the sodium ion battery, which is obtained by mixing the precursor and a sodium source and then sintering.
In a further preferred embodiment, the positive electrode material of the sodium ion battery is a hollow structure.
In a further preferred embodiment, the sodium source is at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate.
In a further preferred embodiment, the sintering process is: heating to 600-1200 ℃ at a heating rate of 3-7 ℃/min, sintering for 8-30 h, and cooling to room temperature at a cooling rate of 2-5 ℃/min.
The invention also provides a sodium ion battery which comprises the positive electrode material.
The invention has the following obvious beneficial effects:
the core of the precursor is copper hydroxide, and at higher temperature, the surface energy of copper hydroxide core particles is larger than the grain boundary energy of the shell because of smaller copper hydroxide core particles, and the mass transfer driving force generated by the energy difference enables Cu element to uniformly enter the shell to react with oxygen to form a novel ternary or multi-element anode material. The hollow structure can relieve stress caused by volume change of materials in the charge and discharge process of the released battery, and provides better cycle stability.
Sintering the precursor to obtain the anode material, and Cu in the layered sodium ion battery anode material 2+ Compared with Ni 2+ The air stability of the material is increased while providing charge compensation, effectively improving the electrochemical properties of the material and reducing the material cost.
The invention adopts the soft template method to prepare the copper hydroxide seed crystal, adopts the coprecipitation method to deposit the shell on the surface of the seed crystal, has simple process and low energy consumption, and can adjust the particle size of the precursor according to the requirement.
Drawings
FIG. 1 is a cross-sectional SEM of a precursor material prepared according to example 1.
Fig. 2 is a cross-sectional SEM image of the positive electrode material prepared in example 1.
Fig. 3 is a Cu element EDS-Mapping spectrum of the positive electrode material prepared in example 2.
Fig. 4 is a Cu element EDS-Mapping spectrum of the positive electrode material prepared in comparative example 2.
Fig. 5 is a cycle performance curve of a battery assembled from the positive electrode materials prepared in example 1 and comparative example 1, respectively.
Fig. 6 is a cycle performance curve of a battery assembled from the positive electrode materials prepared in example 2 and comparative example 2, respectively.
Fig. 7 is a cycle performance curve of a battery assembled from the positive electrode materials prepared in example 3 and comparative example 3, respectively.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
The embodiment comprises the following steps:
(1) Preparation of precursor materials
(1) Preparing a solution:
weighing 13.73 kg copper sulfate pentahydrate, fully mixing with pure hot water, and preparing 55L solution A after complete dissolution, wherein the concentration of copper ions in the solution A is 1.0 mol/L;
preparing 25% industrial ammonia water into a precipitator solution B with the concentration of 1.0 mol/L;
fully mixing and dissolving 27.59 kg hexahydrate nickel sulfate, 45.87 kg ferrous sulfate heptahydrate, 36.795 kg tetrahydrate manganese sulfate and hot pure water to prepare 200L solution C, wherein the molar ratio of nickel, iron and manganese is Ni: fe: mn=25:37.5:37.5;
preparing ethylenediamine into complexing agent solution D with the concentration of 7.5 mol/L;
mixing 32% industrial sodium hydroxide with distilled water to prepare a 5 mol/L precipitant solution E;
(2) preparing copper hydroxide seed crystal: adding 550g of polyethylene glycol 400 soft template into a 100L reaction kettle, then injecting 55L of solution A through a flowmeter pump, uniformly mixing, controlling the temperature of the reaction kettle to be 70 ℃, pumping a precipitant B through a metering pump at the speed of 1L/min at the stirring speed of 500 rpm, and filtering and washing to obtain copper hydroxide crystal seeds after the reaction is finished, wherein the granularity of the copper hydroxide crystal seeds is 4.0 mu m.
(3) Preparing a reaction kettle base solution: adding hot pure water to 1/2 of the volume of a reaction kettle in 300L, controlling the temperature in the kettle to be 70 ℃, stirring at 350 rpm, continuously injecting complexing agent solution D, precipitator solution E and copper hydroxide seed crystal turbid liquid through a flowmeter pump, regulating the initial concentration of the complexing agent to be 6.5 g/L and the initial pH value to be 12, preparing a reaction kettle base solution, opening a gas mass flowmeter and introducing N 2 The gas flow rate is 25L/min, so that the oxygen concentration in the reaction kettle is controlled below 0.5%.
(4) Coprecipitation reaction: continuously adding the solution C, the solution D and the solution E into a reaction kettle in a stirring state through respective corresponding liquid inlet pipes, monitoring the granularity of a reaction system in real time, and stopping the reaction when the granularity reaches 8.0 mu m; the temperature of the reaction system is controlled to be 70 degrees C, pH value to be 12-12.5, the concentration of the complexing agent to be 6.5 g/L and the stirring speed to be 350 rpm in the whole reaction process; and filtering and washing the obtained slurry, drying the qualified solid product in a baking oven at 150 ℃ for 8h, and sieving with a 350-mesh screen to remove iron to obtain the ternary sodium-electricity precursor material with copper hydroxide as crystal nucleus.
(2) Sodium mixed sintering
Weighing 10 g copper hydroxide serving as crystal nucleus ternary sodium-electricity precursor material and 7.9638 g Na 2 CO 3 •H 2 O, mixing for 30 min at a rotating speed of 350 rpm by using a high-speed three-dimensional vibration ball mill, and then spreading the mixed material in a corundum sagger; then controlling the oxygen flow to be 1.5L/min, heating to 850 ℃ at the heating rate of 5 ℃/min, sintering to 24 h, cooling to room temperature at the cooling rate of 3 ℃/min, and sieving with a 400-mesh screen to obtain the sodium-electricity anode material.
FIG. 1 is a cross-sectional SEM image of a ternary sodium-electricity precursor material using copper hydroxide as a crystal nucleus prepared in example 1. As can be seen from the figure, the precursor is core-shell spheroid.
Fig. 2 is an SEM image of a section of the sodium-electricity positive electrode material prepared in example 1. As can be seen from the figure, the cathode material is hollow inside, and the shell is formed by stacking lamellar primary particles.
Comparative example 1
Comparative example 1 differs from example 1 in that: doping of Cu is achieved during co-precipitation, rather than first preparing Cu (OH) 2 And (5) seed crystal. The specific process is as follows:
(1) Precursor preparation
(1) Preparing a solution:
preparing 25% industrial ammonia water into a precipitator solution A with the concentration of 1.0 mol/L;
fully mixing and dissolving 27.59 kg hexahydrate nickel sulfate, 13.73 kg pentahydrate copper sulfate, 45.87 kg heptahydrate ferrous sulfate, 36.795 kg tetrahydrate manganese sulfate and hot pure water to prepare 200L solution B, wherein the molar ratio of nickel, copper, iron and manganese is Ni: cu: fe: mn=2:1:3:1;
preparing ethylenediamine into complexing agent solution C with the concentration of 7.5 mol/L;
mixing 32% industrial sodium hydroxide with distilled water to prepare a precipitant solution D with the concentration of 5 mol/L;
(2) preparing a reaction kettle base solution: adding hot pure water to 1/2 of the volume of a reaction kettle in a reaction kettle of 300L, controlling the temperature in the kettle to be 70 ℃, stirring at 350 rpm, continuously injecting a complexing agent solution C and a precipitator solution D through a flowmeter pump, regulating the initial concentration of the complexing agent to be 6.5 g/L and the initial pH to be 12, preparing a bottom solution of the reaction kettle, opening a gas mass flowmeter, and introducing N 2 The gas flow rate is 25L/min, so that the oxygen concentration in the reaction kettle is controlled below 0.5%.
(3) Coprecipitation reaction: continuously adding the solution A, the solution B, the solution C and the solution D into a reaction kettle in a stirring state through respective corresponding liquid inlet pipes, monitoring the granularity of a reaction system in real time, and stopping the reaction when the granularity reaches 8.0 mu m; the temperature of the reaction system is controlled to be 70 degrees C, pH value to be 12-12.5, the concentration of the complexing agent to be 6.5 g/L and the stirring speed to be 350 rpm in the whole reaction process; filtering and washing the obtained slurry, putting the solid product after qualified washing into a baking oven at 150 ℃ for drying 8h, and sieving with a 350-mesh screen for removing iron to obtain a precursor material.
(2) Sodium mixed sintering
Weigh 10. 10 g precursor material, 7.9638 g Na 2 CO 3 •H 2 O, mixing for 30 min at the rotating speed of 350 rpm by using a high-speed three-dimensional vibration ball mill, and then spreading the mixed material in a corundum sagger; then controlling the oxygen flow to be 1.5L/min, heating to 850 ℃ at the heating rate of 5 ℃/min, sintering to 24 h, cooling to room temperature at the cooling rate of 3 ℃/min, and sieving with a 400-mesh screen to obtain the sodium-electricity anode material.
Example 2
The embodiment comprises the following steps:
(1) Preparation of precursor materials
(1) Preparing a solution:
weighing 62.42 kg copper sulfate pentahydrate, fully mixing with pure hot water, and preparing 100L solution A after complete dissolution, wherein the concentration of copper ions is 2.5 mol/L;
preparing 25% industrial ammonia water into 3.17 mol/L precipitator solution B;
the 69.50 kg ferrous sulfate heptahydrate, 55.75kg manganese sulfate tetrahydrate and hot pure water are fully mixed and dissolved to prepare 300L solution C, and the molar ratio of iron to manganese is Fe: mn=1:1;
preparing ethylenediamine into a complexing agent solution D with the concentration of 6.25 mol/L;
the 32% industrial sodium hydroxide was mixed with distilled water to prepare a 5 mol/L precipitant solution E.
(2) Preparing copper hydroxide seed crystal: adding 3.2 kg lecithin soft template into a 300L reaction kettle, then injecting 100L of solution A through a flowmeter pump, uniformly mixing, controlling the temperature of the reaction kettle to be 50 ℃, pumping solution B through a metering pump at the speed of 1.5L/min at the stirring speed of 500 rpm, and filtering and washing to obtain copper hydroxide crystal seeds after the reaction is finished, wherein the granularity of the copper hydroxide crystal seeds is 10 mu m.
(3) Preparing a reaction kettle base solution: adding hot pure water to 1/2 of the volume of a reaction kettle in a reaction kettle of 300L, controlling the temperature in the kettle to be 60 ℃, stirring at 350 rpm, continuously injecting complexing agent solution D, precipitant solution E and copper hydroxide seed crystal turbid liquid through a flowmeter pump, regulating the initial concentration of the complexing agent to be 5.0 g/L and the initial pH to be 11.5, preparing a reaction kettle base solution, opening a gas mass flowmeter, and introducing N 2 The gas flow rate is 25L/min,the oxygen concentration in the reaction kettle is controlled below 0.5 percent.
(4) Coprecipitation reaction: continuously adding the solution C, the complexing agent and the precipitant into a reaction kettle in a stirring state through respective corresponding liquid inlet pipes, monitoring the granularity of a reaction system in real time, and stopping the reaction when the granularity reaches 15.0 mu m; the temperature of the reaction system is controlled to be 60 degrees C, pH value to be 11.5-12, the concentration of the complexing agent to be 5.5 g/L and the stirring speed to be 300 rpm in the whole reaction process; and filtering and washing the obtained slurry, drying the qualified solid product in a baking oven at 150 ℃ for 8h, and sieving with a 350-mesh screen to remove iron to obtain the binary sodium-electricity precursor material with copper hydroxide as crystal nucleus.
(2) Sodium mixed sintering
Weighing 20 g copper hydroxide as a crystal nucleus binary sodium-electricity precursor material and 14.5436 g Na 2 CO 3 •H 2 O, mixing for 30 min at the rotating speed of 350 rpm by using a high-speed three-dimensional vibration ball mill, and then spreading the mixed material in a corundum sagger; then controlling the oxygen flow to be 2.5L/min, heating to 600 ℃ at a heating rate of 3 ℃/min, sintering to 30h, cooling to room temperature at a cooling rate of 2 ℃/min, and sieving with a 400-mesh screen to obtain the sodium-electricity anode material.
Comparative example 2
Comparative example 2 differs from example 2 in that: doping of Cu is achieved during co-precipitation, rather than first preparing Cu (OH) 2 And (5) seed crystal. The specific process is as follows:
(1) Preparation of sodium-electric precursor material
(1) Preparing a solution:
preparing 25% industrial ammonia water into 3.17 mol/L precipitator solution A;
fully mixing and dissolving 62.42 kg pentahydrate copper sulfate, 69.50 kg ferrous sulfate heptahydrate, 55.75kg tetrahydrate manganese sulfate and hot pure water to prepare 300L solution B, wherein the molar ratio of copper, iron and manganese is Cu: fe: mn=1:1:1;
preparing ethylenediamine into a complexing agent solution C with the concentration of 6.25 mol/L;
the 32% industrial sodium hydroxide was mixed with distilled water to prepare a precipitant solution D of 5 mol/L.
(2) Preparing a reaction kettle base solution: at the position of600 Adding hot pure water into 1/2 of the volume of the reaction kettle, controlling the temperature in the kettle to be 60 ℃, stirring at 350 rpm, continuously injecting a complexing agent solution D and a precipitator solution E through a flowmeter pump, regulating the initial concentration of the complexing agent to be 5.0 g/L and the initial pH to be 11.5, preparing a bottom solution of the reaction kettle, opening a gas mass flowmeter, and introducing N 2 The gas flow rate is 25L/min, so that the oxygen concentration in the reaction kettle is controlled below 0.5%.
(3) Coprecipitation reaction: continuously adding the solution A, the solution B, the solution C and the solution D into a reaction kettle in a stirring state through respective corresponding liquid inlet pipes, monitoring the granularity of a reaction system in real time, and stopping the reaction when the granularity reaches 15.0 mu m; the temperature of the reaction system is controlled to be 60 degrees C, pH value to be 11.5-12, the concentration of the complexing agent to be 5.5 g/L and the stirring speed to be 300 rpm in the whole reaction process; and filtering and washing the obtained slurry, drying the qualified solid product in a baking oven at 150 ℃ for 8h, and sieving with a 350-mesh screen to remove iron to obtain the sodium-electricity precursor material.
(2) Sodium mixed sintering
Weigh 20 g sodium electric precursor material, 14.5436 g Na 2 CO 3 •H 2 O, mixing for 30 min at the rotating speed of 350 rpm by using a high-speed three-dimensional vibration ball mill, and then spreading the mixed material in a corundum sagger; then controlling the oxygen flow to be 2.5L/min, heating to 600 ℃ at a heating rate of 3 ℃/min, sintering to 30h, cooling to room temperature at a cooling rate of 2 ℃/min, and sieving with a 400-mesh screen to obtain the sodium-electricity anode material.
Fig. 3 and 4 are respectively Cu element EDS-Mapping spectra of the sodium-electricity cathode materials prepared in example 2 and comparative example 2. As can be seen from the figure, the cu element distribution was more uniform in example 2 than in comparative example 2.
Example 3
The embodiment comprises the following steps:
(1) Preparation of precursor materials
(1) Preparing a solution:
weighing 12.48 and kg copper sulfate pentahydrate, fully mixing with pure hot water, and preparing 50L solution A after complete dissolution, wherein the concentration of copper ions is 1 mol/L;
preparing 25% industrial ammonia water into 3.17 mol/L precipitator solution B;
fully mixing and dissolving 26.28 kg hexahydrate nickel sulfate, 12.33 kg heptahydrate magnesium sulfate, 41.70 kg heptahydrate ferrous sulfate, 22.30 kg tetrahydrate manganese sulfate, 7.80 kg titanyl sulfate and hot pure water to prepare 200L solution C, wherein the molar ratio of nickel, magnesium, iron, manganese and titanium is Ni: cu: mg: fe: mn: ti=2:1:3:2:1;
preparing ethylenediamine into a complexing agent solution D with the concentration of 6.25 mol/L;
the 32% industrial sodium hydroxide was mixed with distilled water to prepare a 5 mol/L precipitant solution E.
(2) Preparing copper hydroxide seed crystal: 200g of stearic acid soft template is added into a 100L reaction kettle, 50L of solution A is injected through a flowmeter pump, the mixture is uniformly mixed, the temperature of the reaction kettle is controlled to be 50 ℃, the stirring rotation speed is 500 rpm, solution B is pumped into the reaction kettle through a metering pump at the speed of 1.5L/min, after the reaction is completed, copper hydroxide crystal seeds are obtained through filtration and washing, and the granularity of the copper hydroxide crystal seeds is 1 mu m.
(3) Preparing a reaction kettle base solution: adding hot pure water to 1/2 of the volume of a reaction kettle in a reaction kettle of 300L, controlling the temperature in the kettle to be 60 ℃, stirring at 350 rpm, continuously injecting complexing agent solution D, precipitant solution E and copper hydroxide seed crystal turbid liquid through a flowmeter pump, regulating the initial concentration of the complexing agent to be 5.5 g/L and the initial pH to be 11.7, preparing a reaction kettle base solution, opening a gas mass flowmeter, and introducing N 2 The gas flow rate is 25L/min, so that the oxygen concentration in the reaction kettle is controlled below 0.5%.
(4) Coprecipitation reaction: continuously adding the solution C, the complexing agent and the precipitant into a reaction kettle in a stirring state through respective corresponding liquid inlet pipes, monitoring the granularity of a reaction system in real time, and stopping the reaction when the granularity reaches 5.0 mu m; the temperature of the reaction system is controlled to be between 11.2 and 12.2, the concentration of the complexing agent is controlled to be 5.5 g/L, and the stirring speed is controlled to be 300 rpm in the whole reaction process; and filtering and washing the obtained slurry, drying the qualified solid product in a baking oven at 150 ℃ for 8h, and sieving with a 350-mesh screen to remove iron to obtain the quaternary sodium-electricity precursor material with copper hydroxide as crystal nucleus.
(2) Sodium mixed sintering
Weighing 20 g copper hydroxide serving as crystal nucleus quaternary sodium-electricity precursor material and 16.4317 g Na 2 CO 3 •H 2 O, mixing for 30 min at the rotating speed of 350 rpm by using a high-speed three-dimensional vibration ball mill, and then spreading the mixed material in a corundum sagger; then controlling the oxygen flow to be 2.5L/min, heating to 1200 ℃ at the heating rate of 7 ℃/min, sintering for 8 hours, cooling to room temperature at the cooling rate of 5 ℃/min, and sieving with a 400-mesh screen to obtain the sodium-electricity anode material.
Comparative example 3
Comparative example 3 differs from example 3 in that: doping of Cu is achieved during co-precipitation, rather than first preparing Cu (OH) 2 And (5) seed crystal. The specific process is as follows:
(1) Preparation of sodium-electric precursor material
(1) Preparing a solution:
preparing 25% industrial ammonia water into 3.17 mol/L precipitator solution A;
fully mixing and dissolving 12.48 kg copper sulfate pentahydrate, 26.28 kg nickel sulfate hexahydrate, 12.33 kg magnesium sulfate heptahydrate, 41.70 kg ferrous sulfate heptahydrate, 22.30 kg manganese sulfate tetrahydrate, 7.80 kg titanyl sulfate and hot pure water to prepare 300L solution B, wherein the molar ratio of nickel, copper, magnesium, iron, manganese and titanium is Ni: cu: mg: fe: mn: ti=2:1:1:3:2:1;
preparing ethylenediamine into a complexing agent solution C with the concentration of 6.25 mol/L;
the 32% industrial sodium hydroxide was mixed with distilled water to prepare a precipitant solution D of 5 mol/L.
(2) Preparing a reaction kettle base solution: adding hot pure water to 1/2 of the volume of a reaction kettle in a reaction kettle of 300L, controlling the temperature in the kettle to be 60 ℃, stirring at 350 rpm, continuously injecting a complexing agent solution C and a precipitator solution D through a flowmeter pump, regulating the initial concentration of the complexing agent to be 5.5 g/L and the initial pH to be 11.7, preparing a bottom solution of the reaction kettle, opening a gas mass flowmeter, and introducing N 2 The gas flow rate is 25L/min, so that the oxygen concentration in the reaction kettle is controlled below 0.5%.
(3) Coprecipitation reaction: continuously adding the solution A, the solution B, the solution C and the solution D into a reaction kettle in a stirring state through respective corresponding liquid inlet pipes, monitoring the granularity of a reaction system in real time, and stopping the reaction when the granularity reaches 5.0 mu m; the temperature of the reaction system is controlled to be between 11.2 and 12.2, the concentration of the complexing agent is controlled to be 5.5 g/L, and the stirring speed is controlled to be 300 rpm in the whole reaction process; and filtering and washing the obtained slurry, drying the qualified solid product in a baking oven at 150 ℃ for 8h, and sieving with a 350-mesh screen to remove iron to obtain the sodium-electricity precursor material.
(2) Sodium mixed sintering
Weigh 20 g sodium electric precursor material, 16.4317 g Na 2 CO 3 •H 2 O, mixing for 30 min at the rotating speed of 350 rpm by using a high-speed three-dimensional vibration ball mill, and then spreading the mixed material in a corundum sagger; then controlling the oxygen flow to be 2.5L/min, heating to 1200 ℃ at the heating rate of 7 ℃/min, sintering to 8h, cooling to room temperature at the cooling rate of 5 ℃/min, and sieving with a 400-mesh screen to obtain the sodium-electricity anode material.
The positive electrode materials obtained in examples 1 to 3 and comparative examples 1 to 3 were assembled into batteries: according to 9:0.6:0.1:0.3 Respectively weighing a positive electrode material, conductive carbon black (Super P), conductive graphite and a binder (PVDF) according to the mass ratio, grinding uniformly, and adding a solvent (NMP) to prepare electrode slurry; uniformly coating the slurry on an aluminum foil, and drying and cutting the aluminum foil into an electrode plate phi 12 mm; the prepared electrode sheet was assembled into a 2032 button cell in a glove box under argon atmosphere. The battery system of the invention adopts sodium metal as a counter electrode, uses a glass fiber diaphragm of phi 16 mm, and adopts Na ClO of 1 mol/L as electrolyte 4 Dissolved in a 1:1 volume ratio of a mixed solvent of Ethylene Carbonate (EC) and Polycarbonate (PC) plus 5% by volume of diethyl carbonate (DEC). Assembling the positive electrode shell, the electrode plate, the diaphragm, the metal sodium plate, the gasket, the reed and the negative electrode shell in sequence, and pressurizing the packaging machine by 50 MPa and maintaining the pressure by 10 s. The assembled battery is kept stand for 10 h, the electrolyte fully infiltrates the pole piece, and then the 1C cycle performance of the battery under 2.0-4.0V is tested. The results are shown in fig. 5, 6 and 7, respectively.
As can be seen from FIG. 5, the 1C cycle first-turn discharge specific capacity of example 1 was 121.9 mAh/g, the cycle 200 specific discharge capacity was 96.7 mAh/g, and the capacity retention rate was 79.33%. The specific volume of the first-round discharge of 1C of comparative example 1 was 120.2 mAh/g, the specific capacity of the discharge of 200 rounds was 47.9 mAh/g, and the capacity retention was 39.85%.
As can be seen from FIG. 6, the 1C cycle first-turn discharge specific capacity of example 2 was 137 mAh/g, the cycle 200 specific discharge capacity was 118.8 mAh/g, and the capacity retention rate was 86.72%. The 1C first-turn discharge specific volume of comparative example 2 was 137.6 mAh/g, the discharge specific capacity of 200-turn cycles was 74.4 mAh/g, and the capacity retention was 54.07%.
As can be seen from FIG. 7, the discharge specific capacity of the first cycle of 1C cycle of example 3 was 103 mAh/g, the discharge specific capacity of the second cycle was 97.7 mAh/g, and the capacity retention rate was 94.76%. The specific volume of the first-round discharge of 1C of comparative example 3 was 102.0 mAh/g, the specific capacity of the discharge of 200 rounds was 65.9 mAh/g, and the capacity retention rate was 64.61%.
Therefore, the precursor taking the copper hydroxide as the crystal nucleus prepared by the method improves the battery capacity to a certain extent and prolongs the service life of the battery after being sintered into the hollow positive electrode material.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The precursor of the positive electrode material of the sodium ion battery is characterized in that the precursor is of a core-shell structure, the core is copper hydroxide, and the shell is a binary, ternary or multi-element precursor material; the chemical general formula of the binary, ternary or multi-component precursor material is Ni x1 Mg x2 Fe y Mn z1 Ti z2 (OH) 2 Wherein 0.ltoreq.x1.ltoreq.0.5, 0.ltoreq.x2.ltoreq.0.1, 0.3.ltoreq.y 0.7,0.3.ltoreq.z1.ltoreq. 0.7,0.ltoreq.z2.ltoreq.0.1, x1+x2+y+z1+z2=1.
2. The precursor of a positive electrode material for a sodium ion battery according to claim 1, wherein the particle diameter of the core is 1 to 10 μm and the particle diameter of the precursor is 5 to 15 μm.
3. The method for preparing a precursor of a positive electrode material for sodium ion battery according to claim 1 or 2, comprising the steps of:
step S1, preparing copper salt solution; slowly adding the precipitant into a reaction kettle containing copper salt solution and a soft template for reaction, filtering and washing to obtain copper hydroxide seed crystals;
s2, depositing binary, ternary or multi-element precursor materials on the surface of the seed crystal by a coprecipitation method;
and S3, filtering the slurry, washing and drying the solid phase to obtain a precursor.
4. The method according to claim 3, wherein the copper salt is at least one of copper sulfate, copper nitrate, and copper chloride; the precipitant is at least one of ammonia water, sodium hydroxide and potassium hydroxide; the soft template is at least one of polyethylene glycol 400, lecithin and stearic acid.
5. The method of claim 3, wherein the reaction temperature in step S1 is 50-70 ℃.
6. A positive electrode material of a sodium ion battery, which is characterized in that the positive electrode material of the sodium ion battery prepared by the precursor of the positive electrode material of the sodium ion battery according to claim 1 or 2 or the preparation method according to any one of claims 3 to 5 is obtained by mixing and sintering a sodium source.
7. The positive electrode material of a sodium ion battery of claim 6, wherein the sintering process is: heating to 600-1200 ℃ at a heating rate of 3-7 ℃/min, sintering for 8-30 h, and cooling to room temperature at a cooling rate of 2-5 ℃/min.
8. The positive electrode material of a sodium ion battery according to claim 6 or 7, wherein the positive electrode material of the sodium ion battery has a hollow structure.
9. A sodium ion battery comprising the positive electrode material of the sodium ion battery of any one of claims 6-8.
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