CN114349051A - Multi-metal molybdate, preparation method thereof and lithium ion battery - Google Patents
Multi-metal molybdate, preparation method thereof and lithium ion battery Download PDFInfo
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- CN114349051A CN114349051A CN202111676944.7A CN202111676944A CN114349051A CN 114349051 A CN114349051 A CN 114349051A CN 202111676944 A CN202111676944 A CN 202111676944A CN 114349051 A CN114349051 A CN 114349051A
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 69
- 239000002184 metal Substances 0.000 title claims abstract description 69
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 42
- 239000002738 chelating agent Substances 0.000 claims abstract description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 229910015667 MoO4 Inorganic materials 0.000 claims description 34
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 239000007773 negative electrode material Substances 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052742 iron Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910001415 sodium ion Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
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- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229940033123 tannic acid Drugs 0.000 claims description 4
- 235000015523 tannic acid Nutrition 0.000 claims description 4
- 229920002258 tannic acid Polymers 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 9
- -1 lithium carbonate compound Chemical class 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 229940010552 ammonium molybdate Drugs 0.000 description 4
- 235000018660 ammonium molybdate Nutrition 0.000 description 4
- 239000011609 ammonium molybdate Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- IKUPISAYGBGQDT-UHFFFAOYSA-N copper;dioxido(dioxo)molybdenum Chemical compound [Cu+2].[O-][Mo]([O-])(=O)=O IKUPISAYGBGQDT-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
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- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000003780 insertion Methods 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910011274 Li3V Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/006—Compounds containing, besides molybdenum, 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- 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
-
- 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
- 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
- H01M2004/027—Negative electrodes
Abstract
The invention provides a multi-metal molybdate, a preparation method thereof and a lithium ion battery. The preparation method of the multi-metal molybdate comprises the following steps: mixing an A source compound, an M source compound, a molybdenum source compound and a solvent to form a mixed solution, wherein an A element in the A source compound is a monovalent metal element, and an M element in the M source compound is one, more or vacancy in a 3d transition metal element; the mixed solution and the organic chelating agent are sequentially evaporated and dried to obtain dry gel, wherein the moisture content in the dry gel is not more than 15 wt%; and sintering the xerogel in inert atmosphere to obtain the polymetallic molybdate. The multi-metal molybdate prepared by the method has good electronic conductivity, can inhibit the volume from increasing, and improves the structural stability, so that the multi-metal molybdate has good stable cycle performance and excellent rate performance in the application process.
Description
Technical Field
The invention relates to the field of lithium ion battery manufacturing, in particular to a multi-metal molybdate, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, high working voltage, long service life, wide working temperature, no greenhouse gas emission, no memory effect and the like, is widely applied to various intelligent portable and wearable electronic devices, shows an important application prospect in the fields of new energy automobiles and large-scale energy storage, and quickly becomes a key development object of energy storage industries of various countries. Although lithium ion batteries are an indispensable part of today's society, their large-scale application is severely restricted due to the scarcity of lithium resources and maldistribution. Accordingly, we expect to find more renewable resources as alternatives to lithium ion batteries. It is worth noting that sodium and lithium are adjacent elements of the same main group, and have many similar physical and chemical properties, and sodium is the fourth most abundant element in earth crust, which makes sodium ion battery energy storage technology promising as one of the candidate technologies to replace lithium ion battery technology.
The cathode material is used as another key component in the lithium ion battery system, and plays a decisive role in the aspects of the energy density exertion, the cycle performance, the rate capability, the safety and the like of the battery as the cathode. Graphite anodes have many deficiencies as a commercial lithium ion battery anode material: 1. lower specific energy (372mAh g)-1) (ii) a 2. Rate capability of distillers' grains under heavy current; 3. its lower lithium insertion potential (0.1V) and Li in the discharge process of lithium ion battery+The uneven deposition forms lithium dendrites that can pierce the separator causing short circuits that ultimately lead to safety hazards such as battery fires and even explosions. The defects of the graphite cathode are particularly obvious in the aspect of high-power batteries, and the development and the application of the lithium ion battery in the aspect of electric automobiles are seriously restricted. Therefore, we are always looking for next generation lithium ion battery anode materials to replace graphite anodes.
In recent years, lithium ion battery negative electrode materials have been widely explored, and can be classified into the following categories according to their lithium storage mechanisms: 1. the embedded negative electrode material, such as layered graphite, spinel-structured lithium titanate and the like, has the advantages of stable voltage platform and small volume strain in the charge and discharge process, but the specific capacity of the material is usually very low; 2. alloying type negative electrode materials, such as Si, Ge, Sn and the like, are characterized in that huge specific capacity can be released by forming an alloy with Li in the charging and discharging process, but the huge volume change and unstable structure of the electrode material are often accompanied in the process, so that serious capacity attenuation is caused; 3. conversion type negative electrode materials, such as most transition metal oxides, have a lithium insertion potential of 0.5-1V, release a high specific capacity by realizing multi-electron transfer during charge and discharge, but low electronic conductivity, volume expansion during cycling and voltage hysteresis are all main problems faced by transition metal oxides.
The prior art for transition metal oxide lithium ion battery negative electrode materials is as follows:
the existing literature provides a preparation method of a lithium battery metal oxide negative electrode material, which is a doped metal oxide negative electrode material prepared by ball-milling and mixing raw materials of various metals, niobium oxide and tungsten oxide in proportion, heating and tabletting, ball-milling and the like. The lithium ion battery cathode material has stable long cycle performance, but the released specific capacity is lower (220 mAh g)-1)。
Another prior document provides a preparation method of transition metal oxide/graphene in-situ composite, in which graphene oxide is grown in situ on a hydroxide substrate by a hydrothermal method, and the transition metal oxide/graphene composite is obtained by subsequent roasting. As a lithium ion battery cathode material, the volume expansion effect of the lithium ion battery cathode material can be effectively relieved in the charge and discharge processes, and the lithium ion battery cathode material has excellent electrochemical performance.
However, the above prior art has disadvantages that the conversion type negative electrode material has low electron conductivity, which causes severe capacity fade during cycling; the volume change of the conversion type negative electrode material is large in the charge and discharge process, and the structure is unstable.
Disclosure of Invention
The invention mainly aims to provide a multi-metal molybdate, a preparation method thereof and a lithium ion battery, and aims to solve the problems of low electronic conductivity, large volume change and unstable structure of the conventional lithium ion battery cathode material.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a multi-metal molybdate, the method comprising: mixing an A source compound, an M source compound, a molybdenum source compound and a solvent to form a mixed solution, wherein an A element in the A source compound is a monovalent metal element, and an M element in the M source compound is one, more or vacancy in a 3d transition metal element; the mixture of the mixed solution and the organic chelating agent is sequentially evaporated and dried to obtain dry gel, wherein the moisture content in the dry gel is not more than 15 wt%; and sintering the xerogel in inert atmosphere to obtain the multi-metal molybdate.
Furthermore, the mole ratio of the A element in the A source compound, the M element in the M source compound, the molybdenum element in the molybdenum source compound and the organic chelating agent is (1-5): 0.1-5): 3: (2-8).
Further, the element A is selected from one or more of the group consisting of Li, Na, K and Ag, and the source A compound is one or more of the group consisting of oxide, hydroxide, carbonate, sulfate, acetate and nitrate; m element is selected from one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, and M source compound is selected from one or more of oxide, hydroxide, carbonate, sulfate, acetate and nitrate; the organic chelating agent is one or more selected from the group consisting of citric acid, tannic acid, glucose, sucrose, starch, maltose, urea, and melamine.
Further, the evaporation process is carried out under the condition of water bath at the temperature of 70-90 ℃; the temperature in the drying process is 120-160 ℃, and the drying time is 4-6 h.
Further, the sintering process comprises: carrying out primary sintering treatment on the xerogel to obtain a pre-sintered product; and carrying out secondary sintering treatment on the pre-sintered product to obtain the multi-metal molybdate.
Further, the temperature of the first sintering treatment process is 300-400 ℃, and the sintering time is 2-4 hours; the temperature of the second sintering treatment process is 550-850 ℃, and the sintering time is 5-20 hours; preferably, the temperature rise rate of the second sintering treatment process is 5-10 ℃ per minute-1The cooling rate is 5-10 ℃ per minute-1。
In another aspect of the present application, a multi-metal molybdate is provided, the multi-metal molybdate having the general formula AxMy(MoO4)3Wherein A is a monovalent metal element, M is one, more or a vacancy of a 3d transition metal element, 1<x<5，0.1<y<5, the multi-metal molybdate is prepared by the preparation method.
Further, the space group of the polymetallic molybdate is Pnma, cubic crystal structure.
Further, the multimetallic molybdate is selected from Li3M1(MoO4)3、Li2M22(MoO4)3And Li3Ti0.75(MoO4)3One or more of the group consisting of, wherein M1 is selected from the elements V, Fe or Cr, and M2 is selected from the elements Co, Fe, Ni, Zn or Cu.
Yet another aspect of the present application also provides a lithium ion battery or a sodium ion battery comprising a negative electrode material comprising the above-described multimetal molybdate.
By applying the technical scheme of the invention, the sol-gel method can realize the uniform mixing of the raw materials at molecular or atomic level, on one hand, the generation of impurity phases is avoided, on the other hand, the diffusion path of atoms diffusing to a phase forming interface in the high-temperature sintering process is effectively shortened, the material synthesis temperature can be effectively reduced, and the sintering time can be shortened; meanwhile, the addition of the organic chelating agent can improve the utilization rate of the transition metal element and can serve as an organic carbon source. The organic carbon source is carbonized in the high-temperature sintering process and coated on the surface of the compound, so that the electronic conductivity of the compound can be improved, the volume expansion in the charging and discharging process can be relieved, the further growth of primary particles of the compound can be obvious, the route of diffusion of lithium ions or sodium ions in the bulk phase of the compound is shortened, and the inherent stable cycle performance and excellent rate capability of the multi-metal molybdate are ensured to be exerted. On the basis, the multi-metal molybdate prepared by the method has good electronic conductivity, can inhibit the volume from increasing, and improves the structural stability, so that the multi-metal molybdate has good stable cycle performance and excellent rate performance in the application process.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is an XRD pattern of the copper molybdate lithium electrode material prepared in example 1;
fig. 2 is an SEM image of the copper molybdate lithium electrode material prepared in example 1;
FIG. 3 is a charge-discharge curve of the lithium copper molybdate prepared in example 1 as a negative electrode material of a lithium ion battery;
FIG. 4 shows the cycle performance of the lithium copper molybdate prepared in example 1 as a negative electrode material of a lithium ion battery;
fig. 5 is a charge and discharge curve of the lithium copper molybdate obtained in example 4 as a negative electrode material for a sodium ion battery.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the conventional lithium ion battery cathode material has the problems of low electronic conductivity, large volume change and unstable structure. In order to solve the above technical problems, the present application provides a method for preparing a multi-metal molybdate, the method comprising: mixing an A source compound, an M source compound, a molybdenum source compound and a solvent to form a mixed solution, wherein an A element in the A source compound is a monovalent metal element, and an M element in the M source compound is one, more or vacancy in a 3d transition metal element; the mixture of the mixed solution and the organic chelating agent is sequentially evaporated and dried to obtain dry gel, wherein the moisture content in the dry gel is not more than 15 wt%; and sintering the xerogel in inert atmosphere to obtain the multi-metal molybdate.
In the preparation method, the sol-gel method is adopted to realize the uniform mixing of the raw materials at a molecular or atomic level, so that the generation of an impurity phase is avoided, the diffusion path of atoms diffusing to a phase forming interface in the high-temperature sintering process is effectively shortened, the material synthesis temperature is effectively reduced, and the sintering time is shortened; meanwhile, the addition of the organic chelating agent can improve the utilization rate of the transition metal element and can serve as an organic carbon source. The organic carbon source is carbonized in the high-temperature sintering process and coated on the surface of the compound, so that the electronic conductivity of the compound can be improved, the volume expansion in the charging and discharging process can be relieved, the further growth of primary particles of the compound can be obvious, the route of diffusion of lithium ions or sodium ions in the bulk phase of the compound is shortened, and the inherent stable cycle performance and excellent rate capability of the multi-metal molybdate are ensured to be exerted. On the basis, the multi-metal molybdate prepared by the method has good electronic conductivity, can inhibit the volume from increasing, and improves the structural stability, so that the multi-metal molybdate has good stable cycle performance and excellent rate performance in the application process.
In a preferred embodiment, the mole ratio of the A element in the A source compound, the M element in the M source compound, the molybdenum element in the molybdenum source compound and the organic chelating agent is (1-5): 0.1-5): 3- (2-8). The mole number ratio of the element A in the source compound, the element M in the source compound, the molybdenum in the source compound and the organic chelating agent includes but is not limited to the above range, and the limitation of the mole number ratio in the above range is beneficial to further improving and reducing the generation of impurity phases, better controlling the growth of crystal grains and improving the energy density and the specific discharge capacity in the application process of the multi-metal molybdate.
In a preferred embodiment, the a element includes, but is not limited to, one or more of the group consisting of Li, Na, K, and Ag, and the a source compound includes, but is not limited to, one or more of the group consisting of oxide, hydroxide, carbonate, sulfate, acetate, and nitrate; m element includes but is not limited to one or more of the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, M source compound includes but is not limited to one or more of the group consisting of oxide, hydroxide, carbonate, sulfate, acetate and nitrate; the organic chelating agent includes, but is not limited to, one or more of the group consisting of citric acid, tannic acid, glucose, sucrose, starch, maltose, urea, melamine. Compared with other elements, the A elements have higher specific capacity and energy density and wider sources. Compared with other 3d transition metal elements, the M elements and the Mo elements have multiple element valence states, and more electrons can be transferred through an energy storage mechanism of conversion reaction in the charge-discharge process, so that higher specific capacity is released. Therefore, the element A and the element M are beneficial to further improving the specific capacity and the energy density of the multi-metal molybdate in the application process, so that the dynamic performance of the multi-metal molybdate can be improved.
The purpose of the evaporation process is mainly to remove the solvent in the mixed solution, so that the solute is precipitated in the form of sol, as long as the above purpose can be achieved, and the specific temperature is not limited. In a preferred embodiment, the evaporation process is carried out in a water bath at 70-90 ℃. Limiting the temperature of the evaporation process within the above range is beneficial to improving the evaporation rate on one hand and reducing the content of impurities in the gel on the other hand, thereby being beneficial to better controlling the growth of crystal grains and further improving the comprehensive performance of the multi-metal molybdate in the application process.
In a preferred embodiment, the temperature of the drying process is 120-160 ℃, and the drying time is 4-6 h. The temperature and time of the drying process include, but are not limited to, the above ranges, and it is advantageous to improve drying efficiency and moisture removal rate by limiting the temperature and time to the above ranges.
In a preferred embodiment, the sintering process comprises: carrying out primary sintering treatment on the xerogel to obtain a pre-sintered product; and carrying out secondary sintering treatment on the pre-sintered product to obtain the multi-metal molybdate. The xerogel treated by the two sintering treatment processes is beneficial to improving the compactness of the multi-metal molybdate, thereby being beneficial to improving the uniformity of crystal grains, and further being beneficial to improving the structural stability and the long cycle performance. In order to further improve the comprehensive performance of the multi-metal molybdate, the temperature of the first sintering treatment process is preferably 300-400 ℃, and the sintering time is preferably 2-4 h; the temperature of the second sintering treatment process is 550-850 ℃, and the sintering time is 5-20 h. More preferably, the temperature rise rate of the second sintering treatment process is 5-10 ℃ min-1The cooling rate is 5-10 ℃ per minute-1. Limiting the temperature increase rate and the temperature decrease rate of the second sintering treatment within the above ranges is advantageous for improving the crystallinity of the product.
In a second aspect of the present application, there is provided a multimetallic molybdate of the general formula AxMy(MoO4)3Wherein A is a monovalent metal element, M is one, more or a vacancy of a 3d transition metal element, 1<x<5，0<y<5, the multi-metal molybdate is prepared by the preparation method provided by the application.
The multi-metal molybdate prepared by the method has good electronic conductivity, can inhibit the volume from increasing, and improves the structural stability, so that the multi-metal molybdate has good stable cycle performance and excellent rate performance in the application process.
In a preferred embodiment, the multi-metal molybdate has a space group of Pnma, cubic crystal structure. Compared with other crystal structures, the multi-metal molybdate with the crystal structure has better structural stability and electronic conductivity.
In a preferred embodiment, the multimetallic molybdate includes, but is not limited to, Li3M1(MoO4)3、Li2M22(MoO4)3And Li3Ti0.75(MoO4)3One or more of the group consisting of, wherein M1 is selected from the elements V, Fe or Cr, and M2 is selected from the elements Co, Fe, Ni, Zn or Cu. Compared with other compositions, the multi-metal molybdates have more excellent electrochemical performance and dynamic performance.
A third aspect of the present application also provides a lithium ion battery comprising a negative electrode material comprising the multimetallic molybdate provided herein. The multi-metal molybdate provided by the application has better electronic conductivity, can inhibit the volume from becoming larger, and improves the structural stability, so that the multi-metal molybdate serving as a negative electrode material of a lithium ion battery is beneficial to greatly improving the stable cycle performance and the rate capability of the lithium ion battery.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The sol-gel preparation method and application of the multi-metal molybdate electrode material of the embodiment are as follows:
certain amounts of lithium carbonate compound, copper nitrate compound and ammonium molybdate compound are sequentially added into deionized water according to the corresponding mole ratio of 2:2:3 to form a mixed solution.
Mixing citric acid with the above mixed solution, controlling the mole ratio of citric acid to transition metal compounds (copper nitrate compound and ammonium molybdate compound) at 1:1, and magnetically stirring in water bath environment at 90 deg.C until water is completely evaporated to form sol.
The sol was baked in an oven at 160 ℃ for 6h to obtain a xerogel. And placing the xerogel in an agate mortar for primary grinding, and then transferring the xerogel into a ball milling tank for ball milling for 4 hours.
And putting the powder subjected to ball milling into a tube furnace, and performing primary sintering treatment at 300 ℃ in nitrogen or argon for 3 hours to obtain a pre-sintered product. Grinding the pre-sintered product again, placing the pre-sintered product in a tubular furnace, and performing secondary sintering treatment at 650 ℃ in protective atmosphere of nitrogen or argon and the like for 10hThe temperature rise rate in the secondary sintering treatment process is 10 ℃ min-1The cooling rate is 5 ℃ min-1Obtaining polymetallic copper lithium molybdate Li2Cu2(MoO4)3The crystal form is cubic. Fig. 1 is an XRD chart of the copper molybdate lithium electrode material prepared in example 1, and fig. 2 is an SEM chart of the copper molybdate lithium electrode material prepared in example 1.
This application synthesizes Li using a sol-gel process2Cu2(MoO4)3And the material is used as a negative electrode material of a lithium ion battery. The electrochemical performance is tested by adopting a CR2032 button cell, wherein one electrode is prepared polymetallic copper lithium molybdate Li2Cu2(MoO4)3A mixture of a negative electrode material, acetylene black and polyvinylidene fluoride (the weight ratio is 8:1:1), the other electrode is a metal lithium sheet, and the electrolyte is LiPF with the concentration of 1mol/L6Dissolved in a solvent of EC/DMC/EMC (volume ratio 1:1: 1).
The charge and discharge tests were carried out under the conditions that the constant-current charge and discharge voltage range is 0.01-3V and the current density is 100mA/g, and the charge and discharge curves are shown in figure 3. As can be seen from FIG. 3, the first charge-discharge specific capacities were 864mAh/g (charge) and 1287mAh/g (discharge), and the second charge-discharge specific capacities were 840mAh/g and 842 mAh/g.
In the current density range of 100 mA/g-2A/g, the multiplying power performance test is carried out, and the cycle performance is shown in figure 4. As can be seen from FIG. 4, after 100 cycles, the specific discharge capacity is still 825mAh/g, which shows good reversible cycle performance. (discharge capacity retention rate after Nth cycle ═ Nth cycle specific discharge capacity/second cycle specific discharge capacity)
Example 2
The differences from example 1 are: the molar ratio of citric acid to the transition metal compounds (copper nitrate compound and ammonium molybdate compound) in solution C was 0.5:1, and the other steps were the same as in example 1.
The electrochemical performance test method comprises the following steps:
li is obtained by the above method2Cu2(MoO4)3The material is used as a negative electrode material of a lithium ion battery. Adopting CR2032 type fastenerThe electrochemical performance of the battery is tested, wherein one electrode is prepared polymetallic copper lithium molybdate Li2Cu2(MoO4)3A mixture of a negative electrode material, acetylene black and polyvinylidene fluoride (the weight ratio is 8:1:1), the other electrode is a metal lithium sheet, and the electrolyte is LiPF with the concentration of 1mol/L6Dissolved in a solvent of EC/DMC/EMC (volume ratio 1:1: 1). The constant-current charging and discharging voltage range is 0.01-3V. The long cycle test was carried out at a current density of 100 mA/g. And carrying out a multiplying power performance test in a current density range of 100 mA/g-2A/g.
Example 3
The differences from example 1 are: the molar ratio of citric acid to the transition metal compounds (copper nitrate compound and ammonium molybdate compound) in solution C was 4:1, and the other steps were the same as in example 1.
The electrochemical performance test method comprises the following steps:
li is obtained by the above method2Cu2(MoO4)3The material is used as a negative electrode material of a lithium ion battery. The electrochemical performance is tested by adopting a CR2032 button cell, wherein one electrode is prepared polymetallic copper lithium molybdate Li2Cu2(MoO4)3A mixture of a negative electrode material, acetylene black and polyvinylidene fluoride (the weight ratio is 8:1:1), the other electrode is a metal lithium sheet, and the electrolyte is LiPF with the concentration of 1mol/L6Dissolved in a solvent of EC/DMC/EMC (volume ratio 1:1: 1). The constant-current charging and discharging voltage range is 0.01-3V. The long cycle test was carried out at a current density of 100 mA/g. And carrying out a multiplying power performance test in a current density range of 100 mA/g-2A/g.
Example 4
The differences from example 1 are: polymetallic lithium copper molybdate Li2Cu2(MoO4)3The preparation method is the same, but the material is used as the negative electrode material of the sodium-ion battery.
The electrochemical performance test method comprises the following steps:
li is obtained by the above method2Cu2(MoO4)3The material is used as a negative electrode material of a sodium ion battery. Electrochemical performance testing using CR2032 type button cell, whichThe middle electrode is prepared multi-metal lithium copper molybdate Li2Cu2(MoO4)3The negative electrode material, the mixture of acetylene black and polyvinylidene fluoride (weight ratio is 8:1:1), the other electrode is a metal sodium sheet, and the electrolyte is 1mol/L NaClO4Dissolved in a solvent of EC/PC (volume ratio 1: 1).
The charge and discharge are carried out under the conditions that the constant current charge and discharge voltage range is 0.01-3V and the current density is 50mA/g, and the charge and discharge curve is shown in figure 5. As can be seen from FIG. 5, the first charge and discharge specific capacities were 89mAh/g and 168mAh/g, and the second charge and discharge specific capacities were 80mAh/g and 91 mAh/g.
Example 5
The differences from example 1 are: the organic chelating agent is tannic acid.
Example 6
The differences from example 1 are: the organic chelating agent is glucose.
Example 7
The differences from example 1 are: the organic chelating agent is urea.
Example 8
The differences from example 1 are: the organic chelating agent is melamine.
Example 9
The differences from example 1 are: m is Sc, and the prepared multi-metal molybdate is Li3Sc(MoO4)3The crystal form is cubic.
Example 10
The differences from example 1 are: m is Ti, and the prepared multi-metal molybdate is Li3Ti0.75(MoO4)3The crystal form is cubic.
Example 11
The differences from example 1 are: m is V, and the prepared multi-metal molybdate is Li3V(MoO4)3The crystal form is cubic.
Example 12
The differences from example 1 are: m is Cr, and the prepared multi-metal molybdate is Li3Cr(MoO4)3The crystal form is cubic.
Example 13
The differences from example 1 are: the M element is Co, and the prepared multi-metal molybdate is Li2Co2(MoO4)3The crystal form is cubic.
Example 14
The differences from example 1 are: the first sintering treatment is not carried out in the sintering process, and the second sintering treatment is directly carried out. The prepared multi-metal molybdate is Li2Cu2(MoO4)3The crystal form is cubic.
Example 15
The differences from example 1 are: the temperature of the first sintering treatment is 400 ℃, and the sintering time is 2 h. The prepared multi-metal molybdate is Li2Cu2(MoO4)3The crystal form is cubic.
Example 16
The difference from example 1 is that the temperature of the first sintering treatment was 200 ℃ and the sintering time was 4 hours. The prepared multi-metal molybdate is Li2Cu2(MoO4)3The crystal form is cubic.
Example 17
The differences from example 1 are: the temperature of the second sintering treatment is 550 ℃, the sintering time is 20h, wherein the heating rate is 10 ℃ min-1The cooling speed is 5 ℃ min-1. The prepared multi-metal molybdate is Li2Cu2(MoO4)3The crystal form is cubic.
Example 18
The differences from example 1 are: the temperature of the second sintering treatment is 850 ℃, the sintering time is 5h, wherein the heating rate is 10 ℃ min-1The cooling speed is 5 ℃ min-1. The prepared multi-metal molybdate is Li2Cu2(MoO4)3The crystal form is cubic.
Example 19
The differences from example 1 are: the temperature of the second sintering treatment is 500 ℃, the sintering time is 5h, wherein the temperature rise speed is highThe rate is 10 ℃ min-1The cooling speed is 5 ℃ min-1. The prepared multi-metal molybdate is Li2Cu2(MoO4)3The crystal form is cubic.
Example 20
The differences from example 1 are: the heating rate is 5 ℃ min-1The cooling speed is 10 ℃ min-1. The prepared multi-metal molybdate is Li2Cu2(MoO4)3The crystal form is cubic.
Comparative example 1
The differences from example 1 are: the preparation process of the prepared copper lithium molybdate material adopts the steps without adding an organic chelating agent, and the other steps are the same as those of the example 1.
The performance test results of the lithium ion battery negative electrode materials of examples 1 to 20 and comparative example 1 are shown in table 1.
TABLE 1
From the data in table 1, when the content of the organic carbon source citric acid is properly increased, the first charge capacity, the first coulombic efficiency, the cycle performance and the multiplying power of the sample are remarkably improved; when the content of the organic carbon source citric acid is excessively increased, the cycle performance and the rate performance of the organic carbon source citric acid are reduced to a certain degree. The thicker carbon layer can hinder the transmission of lithium ions and simultaneously reduce the specific capacity of the whole copper lithium molybdate negative electrode material.
From example 1 and comparative example 1, it is seen that the carbon layer formed by in-situ coating in the sol-gel synthesis method can improve the electronic conductivity of the material on one hand, and can relieve the volume expansion in the charge and discharge processes on the other hand, thereby stabilizing the structure of the material and realizing excellent electrochemical performance.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the multi-metal molybdate prepared by the method has good electronic conductivity, can inhibit the volume from increasing, and improves the structural stability, so that the multi-metal molybdate has good stable cycle performance and excellent rate performance in the application process.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing multi-metal molybdate, which is characterized by comprising the following steps:
mixing an A source compound, an M source compound, a molybdenum source compound and a solvent to form a mixed solution, wherein an A element in the A source compound is a monovalent metal element, and an M element in the M source compound is one, more or vacancy in a 3d transition metal element;
the mixture of the mixed solution and the organic chelating agent is sequentially evaporated and dried to obtain dry gel, wherein the moisture content in the dry gel is not more than 15 wt%;
and sintering the xerogel in inert atmosphere to obtain the multi-metal molybdate.
2. The method for preparing a polymetallic molybdate according to claim 1, wherein the molar ratio of the element A in the A source compound, the element M in the M source compound, the molybdenum in the molybdenum source compound and the organic chelating agent is (1-5): 0.1-5): 3 (2-8).
3. The method for preparing multimetallic molybdate according to claim 1 or 2, wherein the a element is selected from one or more of the group consisting of Li, Na, K and Ag, and the a source compound is one or more of the group consisting of oxide, hydroxide, carbonate, sulfate, acetate and nitrate;
the M element is selected from one or more of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, and the M source compound is selected from one or more of oxide, hydroxide, carbonate, sulfate, acetate and nitrate;
the organic chelating agent is one or more selected from the group consisting of citric acid, tannic acid, glucose, sucrose, starch, maltose, urea, and melamine.
4. The method for preparing polymetallic molybdate according to claim 1, wherein the evaporation process is carried out in a water bath at 70-90 ℃;
the temperature in the drying process is 120-160 ℃, and the drying time is 4-6 h.
5. The method of claim 1, wherein the sintering process comprises:
carrying out primary sintering treatment on the xerogel to obtain a pre-sintered product;
and carrying out secondary sintering treatment on the pre-sintered product to obtain the multi-metal molybdate.
6. The method for preparing polymetallic molybdate according to claim 5, wherein the temperature of the first sintering treatment process is 300-400 ℃, and the sintering time is 2-4 h; the temperature of the second sintering treatment process is 550-850 ℃, and the sintering time is 5-20 hours;
preferably, the temperature rise rate of the second sintering treatment process is 5-10 ℃ min-1The cooling rate is 5-10 ℃ per minute-1。
7. The multi-metal molybdate is characterized by adopting a general formula AxMy(MoO4)3Wherein A is a monovalent metal element, M is one, more or a vacancy of a 3d transition metal element, 1<x<5，0<y<5, and the polymetallic molybdate is prepared by the preparation method of any one of claims 1 to 6.
8. The multimetallic molybdate of claim 7, wherein the multimetallic molybdate has a space group Pnma, cubic crystal structure.
9. The multimetallic molybdate according to claim 8, wherein the multimetallic molybdate is selected from Li3M1(MoO4)3、Li2M22(MoO4)3And Li3Ti0.75(MoO4)3One or more of the group consisting of, wherein M1 is selected from the elements V, Fe or Cr, and M2 is selected from the elements Co, Fe, Ni, Zn or Cu.
10. A lithium or sodium ion battery comprising a negative electrode material, characterized in that the negative electrode material comprises the multimetallic molybdate of any one of claims 7 to 9.
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| CN114824255A (en) * | 2022-06-27 | 2022-07-29 | 天鹏锂能技术(淮安)有限公司 | Nickel molybdate lithium electrode material, preparation method thereof, positive plate and high-temperature lithium battery |
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