CN106992294B - High-voltage lithium nickel manganese oxide positive electrode composite material, preparation method thereof and lithium ion battery - Google Patents
High-voltage lithium nickel manganese oxide positive electrode composite material, preparation method thereof and lithium ion battery Download PDFInfo
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- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000002608 ionic liquid Substances 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 150000002815 nickel Chemical class 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002696 manganese Chemical class 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 11
- -1 1-ethyl-3-methylimidazolium tetrafluoroborate Chemical compound 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- LLMOLYDGTPLUSB-UHFFFAOYSA-N 2-aminoethyl 2-hydroxypropanoate Chemical compound CC(O)C(=O)OCCN LLMOLYDGTPLUSB-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 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
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 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
- WRGOQTYIHFPQKZ-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;2-hydroxypropanoate Chemical compound CC(O)C([O-])=O.OCC[NH2+]CCO WRGOQTYIHFPQKZ-UHFFFAOYSA-N 0.000 claims description 3
- IDOGARCPIAAWMC-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;acetate Chemical compound CC(O)=O.OCCNCCO IDOGARCPIAAWMC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- BOZAGLYGUSSJHG-UHFFFAOYSA-N formic acid;2-(2-hydroxyethylamino)ethanol Chemical compound OC=O.OCCNCCO BOZAGLYGUSSJHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 239000011295 pitch Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 28
- 239000010410 layer Substances 0.000 description 24
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 13
- 229910052804 chromium Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 8
- 239000010405 anode material Substances 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000012071 phase Substances 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
- 238000005253 cladding Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention discloses a preparation method of a high-voltage lithium nickel manganese oxide positive electrode composite material, the high-voltage lithium nickel manganese oxide positive electrode composite material prepared by the preparation method and a lithium ion battery using the high-voltage lithium nickel manganese oxide positive electrode composite material, wherein the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material comprises the following steps: dissolving lithium salt, M source compound, nickel salt and manganese salt in deionized water, and dropwise adding the deionized water into ionic liquid to obtain a solution; aging the solution to obtain a first product; performing pre-decomposition treatment and sintering treatment on the first product to obtain a second product, wherein the second product is lithium nickel manganese oxide particles doped with M ions; and mixing the second product with a carbon source compound, and coating a carbon layer on the surface of the second product to obtain the high-voltage lithium nickel manganese oxide positive electrode composite material. According to the technical scheme, the high-voltage lithium nickel manganese oxide positive electrode composite material with uniform particle distribution and excellent electrochemical performance can be prepared.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a high-voltage lithium nickel manganese oxide positive electrode composite material, the high-voltage lithium nickel manganese oxide positive electrode composite material prepared by the preparation method and a lithium ion battery using the high-voltage lithium nickel manganese oxide positive electrode composite material.
Background
The lithium ion battery can provide high energy density, and also has the advantages of safety, environmental protection and long service life. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, electrolyte and the like. The positive electrode material is used as an important component of the lithium ion battery, and is very necessary to select a positive electrode material which has excellent performance, wide source, safety and environmental protection.
Lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) Has higher energy and power density, and is a novel anode material. Moreover, the method can also be further carried out by doping anions and cations and coating the surfaceOne-step lifting of lithium nickel manganese oxide (LiNi)0.5Mn1.5O4) The structure and the electrochemical performance of the anode composite material are obtained. Currently, as a method for preparing a positive electrode composite material, a high-temperature solid phase method is generally used. However, the positive electrode composite material prepared by the high-temperature solid-phase method generally has the defects of non-uniform material and poor performance.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a high-voltage lithium nickel manganese oxide positive electrode composite material, and aims to prepare the high-voltage lithium nickel manganese oxide positive electrode composite material with uniform particle distribution and excellent electrochemical performance.
In order to achieve the purpose, the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material provided by the invention comprises the following steps:
dissolving lithium salt, M source compound, nickel salt and manganese salt in deionized water, and dropwise adding the deionized water into ionic liquid to obtain a solution;
aging the solution to obtain a first product;
performing pre-decomposition treatment and sintering treatment on the first product to obtain a second product, wherein the second product is lithium nickel manganese oxide particles doped with M ions;
and mixing the second product with a carbon source compound, and coating a carbon layer on the surface of the second product to obtain the high-voltage lithium nickel manganese oxide positive electrode composite material.
Preferably, before the step of dissolving the lithium salt, the M source compound, the nickel salt, and the manganese salt in deionized water and adding the solution dropwise into the ionic liquid, the method further comprises:
lithium salt, M source compound, nickel salt and manganese salt are configured according to the molar ratio of Li to M to Ni to Mn (0.95-1.15) to x (0.4-0.5) to (1.4-1.5), wherein x is more than 0 and less than or equal to 0.2.
Preferably, the ionic liquid comprises any one of diethanolamine lactate, diethanolamine formate, ethanolamine lactate, diethanolamine acetate, and 1-ethyl-3-methylimidazolium tetrafluoroborate.
Preferably, the temperature of the pre-decomposition treatment is 400-500 ℃, and the time of the pre-decomposition treatment is 6-8 h.
Preferably, the sintering treatment temperature is 800-900 ℃, and the sintering treatment time is 10-12 h.
Preferably, the lithium salt includes at least one of lithium acetate, lithium oxalate, lithium carbonate, and lithium nitrate; the nickel salt comprises at least one of nickel acetate, nickel oxalate, nickel sulfate and nickel nitrate; the manganese salt comprises at least one of manganese acetate, manganese oxalate, manganese sulfate and manganese nitrate.
Preferably, the M source compound comprises any one of chloride salts of four elements of Al, Fe, Cr and Ga or any one of nitrate salts of four elements of Al, Fe, Cr and Ga.
Preferably, the carbon source compound includes at least one of sucrose, glucose, pitch, graphene, and acetylene black.
The invention also provides a high-voltage lithium nickel manganese oxide positive electrode composite material, which is prepared by the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material, and the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material comprises the following steps:
dissolving lithium salt, M source compound, nickel salt and manganese salt in deionized water, and dropwise adding the deionized water into ionic liquid to obtain a solution;
aging the solution to obtain a first product;
performing pre-decomposition treatment and sintering treatment on the first product to obtain a second product, wherein the second product is lithium nickel manganese oxide particles doped with M ions;
and mixing the second product with a carbon source compound, and coating a carbon layer on the surface of the second product to obtain the high-voltage lithium nickel manganese oxide positive electrode composite material.
The invention further provides a lithium ion battery which comprises an anode, wherein the anode comprises the high-voltage lithium nickel manganese oxide anode composite material.
According to the technical scheme, the high-voltage lithium nickel manganese oxide positive electrode composite material can be prepared, and comprises lithium nickel manganese oxide particles and a carbon layer coated on the surfaces of the lithium nickel manganese oxide particles, wherein M ions are doped in the lithium nickel manganese oxide particles, and the M ions are Al ions, Fe ions, Cr ions or Ga ions. Because the lithium nickel manganese oxide has high voltage characteristic, the lithium nickel manganese oxide can generate side reaction with electrolyte, so that the lithium nickel manganese oxide anode material has poor cycle performance and fast capacity attenuation. After the carbon layer cladding is on the surface of nickel lithium manganate particle, can prevent that electrolyte from passing the carbon layer and reacting with nickel lithium manganate particle, improve this high voltage nickel lithium manganate positive electrode composite's chemical stability to promote this high voltage nickel lithium manganate positive electrode composite's cyclicity performance, reduced capacity decay speed. In addition, after M ions (the M ions are ions of one element of Al, Fe, Cr and Ga) are doped in the lithium nickel manganese oxide particles, the electrochemical properties of the high-voltage lithium nickel manganese oxide positive electrode composite material, such as rate capability, cycle performance and the like, can be further improved.
Specifically, after M ions (the M ions are ions of one element of Al, Fe, Cr and Ga) are doped in the lithium nickel manganese oxide particles, the ion diffusion coefficient and the structural stability of the high-voltage lithium nickel manganese oxide positive electrode composite material can be improved, so that the rate capability, the cycle performance and the like of the high-voltage lithium nickel manganese oxide positive electrode composite material are realized.
Furthermore, the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material adopts an ionic thermal synthesis method, and uses the ionic liquid to replace conventional water or organic solvent as a reaction medium, so that ions of various raw materials (lithium salt, M source compound, nickel salt and manganese salt) can be effectively dispersed, the ions of various raw materials can be uniformly mixed at a molecular level, meanwhile, the diffusion mixing rate of the ions of various raw materials is greatly improved, the impurity phase in the prepared high-voltage lithium nickel manganese oxide positive electrode composite material is effectively reduced, and the uniformity of the high-voltage lithium nickel manganese oxide positive electrode composite material is improved. In addition, it can be understood that the higher temperature solid phase method of the preparation method also reduces energy consumption.
In addition, the preparation method of the high-voltage lithium nickel manganese oxide cathode composite material can also effectively avoid Mn3+The high-voltage lithium nickel manganese oxide positive electrode composite material has the advantages that the capacity of the high-voltage lithium nickel manganese oxide positive electrode composite material is effectively improved, and the high-rate discharge performance of the high-voltage lithium nickel manganese oxide positive electrode composite material is improved. In addition, the preparation method of the high-voltage lithium nickel manganese oxide cathode composite material has the advantages of mild conditions, low steam pressure, good thermal stability, high ionic conductivity, various ionic liquids, recyclability and the like, thereby greatly facilitating industrial production and improving the practicability of the invention.
Specifically, the high-voltage lithium nickel manganese oxide positive electrode composite material prepared by the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material has good uniformity and morphology, can obtain high tap density, can eliminate impurity phases and obtain high conductivity and high specific capacity because various raw material ions can be uniformly mixed and completely reacted at a molecular level, and is mild in preparation conditions, numerous in advantages and easy for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a flow chart illustrating the steps of a method for preparing a high voltage lithium nickel manganese oxide positive electrode composite material according to the present invention;
FIG. 2 is an electron scanning electron micrograph of the positive electrode material;
FIG. 3 is an electron scanning electron microscope image of the high-voltage lithium nickel manganese oxide positive electrode composite material of the invention;
FIG. 4 shows LiCr as a high-voltage lithium nickel manganese oxide positive electrode composite material0.05Ni0.475Mn1.475O4And positive electrode material LiNi0.5Mn1.5O4Cyclic voltammogram of (a);
FIG. 5 shows LiCr as a high-voltage lithium nickel manganese oxide positive electrode composite material0.05Ni0.475Mn1.475O4And positive electrode material LiNi0.5Mn1.5O450-cycle performance plot at 0.5C rate.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a preparation method of a high-voltage lithium nickel manganese oxide positive electrode composite material, and aims to prepare the high-voltage lithium nickel manganese oxide positive electrode composite material with uniform particle distribution and excellent electrochemical performance, so as to be applied to a lithium ion battery.
Referring to fig. 1, the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material includes the following steps:
and S100, preparing lithium salt, M source compound, nickel salt and manganese salt according to the molar ratio of Li to M to Ni to Mn (0.95-1.15) to x (0.4-0.5) to (1.4-1.5), wherein x is more than 0 and less than or equal to 0.2. Wherein:
the lithium salt includes at least one of lithium acetate, lithium oxalate, lithium carbonate, and lithium nitrate.
The M source compound comprises any one of chloride salts of four elements of Al, Fe, Cr and Ga or any one of nitrate salts of four elements of Al, Fe, Cr and Ga.
The nickel salt comprises at least one of nickel acetate, nickel oxalate, nickel sulfate and nickel nitrate.
The manganese salt comprises at least one of manganese acetate, manganese oxalate, manganese sulfate and manganese nitrate.
The molar ratio x of the M ions in the M source compound is greater than zero and less than or equal to 0.2, which can effectively improve the ion diffusion coefficient, so that the structural stability of the high-voltage lithium nickel manganese oxide positive electrode composite material is effectively improved.
And step S200, dissolving lithium salt, M source compound, nickel salt and manganese salt in deionized water, and dropwise adding the deionized water into the ionic liquid to obtain a solution.
Specifically, firstly, dissolving the prepared lithium salt, M source compound, nickel salt and manganese salt in deionized water to obtain a mixed solution, then dropwise adding the mixed solution into ionic liquid under a stirring state, and finally dropwise adding a reducing agent into the ionic liquid to obtain the solution. Wherein the content of the first and second substances,
the ionic liquid comprises any one of diethanolamine lactate, diethanolamine formate, ethanolamine lactate, diethanolamine acetate and 1-ethyl-3-methylimidazolium tetrafluoroborate.
The ionic liquid has extremely low vapor pressure, higher thermal stability and adjustable dissolving capacity, and can be widely applied to the fields of organic synthesis, separation and purification as a green medium for replacing the traditional volatile organic solvent; in addition, the electrolyte has the advantages of high conductivity, wide stable electrochemical window, adjustable acidity and alkalinity and the like, and can be used as a novel electrolyte and a high-efficiency catalyst to be applied to the research fields of catalytic chemistry and electrochemistry; moreover, the nano-material has the advantages of low coordination capacity, small interfacial tension and interfacial energy, high orderliness due to easy formation of hydrogen bonds and the like, and can be used for preparing nano-materials with special shapes, and can be used as a medium and a template.
According to the invention, the ionic liquid replaces conventional water or an organic solvent to be used as a reaction medium, so that ions of various raw materials (lithium salt, M source compound, nickel salt and manganese salt) can be effectively dispersed, the ions of the raw materials can be uniformly mixed at a molecular level, and meanwhile, the diffusion mixing rate of the ions of the raw materials can be greatly increased, so that the impurity phase in the prepared high-voltage lithium nickel manganese oxide positive electrode composite material can be effectively reduced, and the uniformity of the high-voltage lithium nickel manganese oxide positive electrode composite material is improved.
The reducing agent comprises any one of ascorbic acid, citric acid and malic acid, has reducibility, and can effectively prevent raw material ions from being oxidized by oxygen in the air, namely, the raw material ions are prevented from being oxidized and damaged by the air, so that the excellent performance of the prepared high-voltage lithium nickel manganese oxide cathode composite material is ensured.
In addition, the dropping and stirring process can prevent the local concentration from being too high, so that ions are dispersed in the solution more uniformly, good conditions are provided for subsequent physical and chemical changes, and the obtained substances are more uniform.
And step S300, carrying out aging treatment on the solution to obtain a first product.
Specifically, the solution is placed in a reaction kettle and is aged for 2-40 h at constant temperature under the nitrogen atmosphere, and the first product (in the form of solid precipitate) is obtained. After centrifugal separation, the first product is placed in a vacuum drying oven, and is dried and dewatered at the temperature of 100-130 ℃ under the nitrogen atmosphere.
The aging treatment promotes the growth of crystals and the completion of the reaction between the ions of the respective raw materials.
It can be understood that the nitrogen atmosphere can prevent each raw material ion from contacting with oxygen in the air, and prevent each raw material ion from being damaged by oxidation. In addition to nitrogen, an inert gas such as argon may be used.
And S400, performing pre-decomposition treatment and sintering treatment on the first product to obtain a second product, wherein the second product is lithium nickel manganese oxide particles doped with M ions.
Specifically, before the first product is subjected to pre-decomposition treatment and sintering treatment, the first product is washed, and then the first product is placed at 80-100 ℃ and dried for 8-10 h at constant temperature.
The pre-decomposition treatment is to place the first product after the constant temperature drying treatment in a tubular furnace for a pre-decomposition reaction of 6-8 h at 400-500 ℃.
The sintering treatment is to sinter the product after the pre-decomposition treatment for 10 to 12 hours at the temperature of between 800 and 900 ℃ so as to carry out pyrolysis reaction.
And finally, cooling along with the furnace to obtain the second product, namely the lithium nickel manganese oxide material doped with M ions.
And S500, mixing the second product with a carbon source compound, and coating a carbon layer on the surface of the second product to obtain the high-voltage lithium nickel manganese oxide cathode composite material.
Specifically, the second product (i.e., the lithium nickel manganese oxide material doped with M ions) and a carbon source compound are ground and mixed until the mixture is uniformly dispersed, so that the surface of the second product is coated with the carbon source compound. And then, placing the lithium ion battery anode material in a tubular furnace, and carrying out high-temperature treatment under a protective atmosphere to obtain the high-voltage lithium nickel manganese oxide anode composite material, namely the core-shell type high-voltage lithium ion battery anode material. Wherein the carbon source compound comprises at least one of sucrose, glucose, pitch, graphene and acetylene black.
It will be appreciated that the protective atmosphere prevents the substance from reacting with oxygen in the air, thereby preventing the substance from being damaged by oxidation. The protective atmosphere may be an inert gas such as nitrogen or argon.
By adopting the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material, the high-voltage lithium nickel manganese oxide positive electrode composite material can be prepared, and comprises lithium nickel manganese oxide particles and a carbon layer coated on the surfaces of the lithium nickel manganese oxide particles, wherein M ions are doped in the lithium nickel manganese oxide particles, and the M ions are Al ions, Fe ions, Cr ions or Ga ions. Because the lithium nickel manganese oxide has high voltage characteristic, the lithium nickel manganese oxide can generate side reaction with electrolyte, so that the lithium nickel manganese oxide anode material has poor cycle performance and fast capacity attenuation. After the carbon layer cladding is on the surface of nickel lithium manganate particle, can prevent that electrolyte from passing the carbon layer and reacting with nickel lithium manganate particle, improve this high voltage nickel lithium manganate positive electrode composite's chemical stability to promote this high voltage nickel lithium manganate positive electrode composite's cyclicity performance, reduced capacity decay speed. In addition, after M ions (the M ions are ions of one element of Al, Fe, Cr and Ga) are doped in the lithium nickel manganese oxide particles, the electrochemical properties of the high-voltage lithium nickel manganese oxide positive electrode composite material, such as rate capability, cycle performance and the like, can be further improved.
Specifically, after M ions (the M ions are ions of one element of Al, Fe, Cr and Ga) are doped in the lithium nickel manganese oxide particles, the ion diffusion coefficient and the structural stability of the high-voltage lithium nickel manganese oxide positive electrode composite material can be improved, so that the rate capability, the cycle performance and the like of the high-voltage lithium nickel manganese oxide positive electrode composite material are realized.
Furthermore, the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material adopts an ionic thermal synthesis method, and uses the ionic liquid to replace conventional water or organic solvent as a reaction medium, so that ions of various raw materials (lithium salt, M source compound, nickel salt and manganese salt) can be effectively dispersed, the ions of various raw materials can be uniformly mixed at a molecular level, meanwhile, the diffusion mixing rate of the ions of various raw materials is greatly improved, the impurity phase in the prepared high-voltage lithium nickel manganese oxide positive electrode composite material is effectively reduced, and the uniformity of the high-voltage lithium nickel manganese oxide positive electrode composite material is improved. In addition, it can be understood that the higher temperature solid phase method of the preparation method also reduces energy consumption.
In addition, the preparation method of the high-voltage lithium nickel manganese oxide cathode composite material can also effectively avoid Mn3+The high-voltage lithium nickel manganese oxide positive electrode composite material has the advantages that the capacity of the high-voltage lithium nickel manganese oxide positive electrode composite material is effectively improved, and the high-rate discharge performance of the high-voltage lithium nickel manganese oxide positive electrode composite material is improved. In addition, the preparation method of the high-voltage lithium nickel manganese oxide cathode composite material has the advantages of mild conditions, low steam pressure, good thermal stability, high ionic conductivity, various ionic liquids, recyclability and the like, thereby greatly facilitating industrial production and improving the practicability of the invention.
Specifically, the high-voltage lithium nickel manganese oxide positive electrode composite material prepared by the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material has good uniformity and morphology, can obtain high tap density, can eliminate impurity phases and obtain high conductivity and high specific capacity because various raw material ions can be uniformly mixed and completely reacted at a molecular level, and is mild in preparation conditions, numerous in advantages and easy for industrial production.
The invention also provides a high-voltage lithium nickel manganese oxide positive electrode composite material.
The high-voltage lithium nickel manganese oxide positive electrode composite material is prepared by the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material, the high-voltage lithium nickel manganese oxide positive electrode composite material comprises lithium nickel manganese oxide particles and a carbon layer coated on the surfaces of the lithium nickel manganese oxide particles, M ions are doped in the lithium nickel manganese oxide particles, and the M ions are Al ions, Fe ions, Cr ions or Ga ions.
The chemical general formula of the high-voltage lithium nickel manganese oxide positive electrode composite material is as follows: LiMxNi0.5-0.5xMn1.5-0.5xO4And @ C, wherein x is more than 0 and less than or equal to 0.2.
The high-voltage lithium nickel manganese oxide positive electrode composite material comprises lithium nickel manganese oxide particles and a carbon layer coated on the surfaces of the lithium nickel manganese oxide particles, wherein M ions are doped in the lithium nickel manganese oxide particles, and the M ions are Al ions, Fe ions, Cr ions or Ga ions. Because the lithium nickel manganese oxide has high voltage characteristic, the lithium nickel manganese oxide can generate side reaction with electrolyte, so that the lithium nickel manganese oxide anode material has poor cycle performance and fast capacity attenuation. After the carbon layer cladding is on the surface of nickel lithium manganate particle, can prevent that electrolyte from passing the carbon layer and reacting with nickel lithium manganate particle, improve this high voltage nickel lithium manganate positive electrode composite's chemical stability to promote this high voltage nickel lithium manganate positive electrode composite's cyclicity performance, reduced capacity decay speed. In addition, after M ions (the M ions are ions of one element of Al, Fe, Cr and Ga) are doped in the lithium nickel manganese oxide particles, the electrochemical properties of the high-voltage lithium nickel manganese oxide positive electrode composite material, such as rate capability, cycle performance and the like, can be further improved.
Specifically, after M ions (the M ions are ions of one element of Al, Fe, Cr and Ga) are doped in the lithium nickel manganese oxide particles, the ion diffusion coefficient and the structural stability of the high-voltage lithium nickel manganese oxide positive electrode composite material can be improved, so that the rate capability, the cycle performance and the like of the high-voltage lithium nickel manganese oxide positive electrode composite material are realized.
The thickness of the carbon layer is 2 nm-50 nm.
In the technical scheme of the embodiment, the thickness of the carbon layer is 2 nm-50 nm, so that the carbon layer can effectively prevent the lithium nickel manganese oxide from contacting with the electrolyte to generate side reaction.
Furthermore, the nanoscale carbon layer also has a nanometer effect, so that the electronic conductivity and the ion diffusion coefficient of the high-voltage lithium nickel manganese oxide positive electrode composite material can be improved, and the rate capability of the high-voltage lithium nickel manganese oxide positive electrode composite material is further improved.
The carbon layers are all continuous layers.
In the technical scheme of this embodiment, the carbon layer is continuous layer, and like this, the carbon layer can wrap up in nickel lithium manganate particle surface continuously, forms continuous protective layer at nickel lithium manganate particle surface to reduce the side reaction of nickel lithium manganate particle and electrolyte.
The carbon layer coats the whole surface of the lithium nickel manganese oxide particles.
In the technical scheme of this embodiment, the carbon layer cladding is in the whole surface of nickel lithium manganate granule, forms complete protective layer on nickel lithium manganate granule surface to reduce the side reaction of nickel lithium manganate granule and electrolyte.
Specifically, referring to fig. 2 and 3, as can be seen from fig. 2 and 3, the uniformity of the modified high-voltage lithium nickel manganese oxide positive electrode composite material is better. Therefore, the method is greatly beneficial to the subsequent processing process of the lithium ion battery, and the obtained lithium ion battery has higher consistency and more excellent comprehensive performance.
Referring to fig. 4, it can be seen from fig. 4 that the ratio of the oxidation peak current to the reduction peak current of the unmodified high voltage lithium nickel manganese oxide positive electrode composite material is closer to 1, indicating that: after modification, the structure of the high-voltage lithium nickel manganese oxide positive electrode composite material is more stable in the charging and discharging process, the reversibility of lithium ion intercalation/deintercalation is stronger, the coulombic efficiency is better, and the battery can obtain better cycle performance.
Referring to fig. 5, it can be seen from fig. 5 that the modified high-voltage lithium nickel manganese oxide positive electrode composite material has a higher specific discharge capacity and a higher capacity retention rate.
The invention also provides a lithium ion battery (not shown in the figure), which comprises a positive electrode, wherein the positive electrode comprises the high-voltage lithium nickel manganese oxide positive electrode composite material.
Since the lithium ion battery adopts all technical solutions of all the embodiments, at least all the beneficial effects brought by the technical solutions of the embodiments are achieved, and no further description is given here.
The lithium ion battery also comprises a negative electrode, and electrolyte and a diaphragm which are arranged between the positive electrode and the negative electrode.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (9)
1. The preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material is characterized by comprising the following steps of:
dissolving lithium salt, M source compound, nickel salt and manganese salt in deionized water, and dropwise adding the deionized water into ionic liquid to obtain a solution;
aging the solution to obtain a first product;
performing pre-decomposition treatment and sintering treatment on the first product to obtain a second product, wherein the second product is lithium nickel manganese oxide particles doped with M ions;
mixing the second product with a carbon source compound, carrying out heat treatment under a protective atmosphere, and coating a carbon layer on the surface of the second product to obtain the high-voltage lithium nickel manganese oxide positive electrode composite material;
the M source compound comprises any one of chloride salts of Al and Ga elements or any one of nitrate salts of Al and Ga elements.
2. The method of claim 1, wherein the step of dissolving the lithium salt, the M source compound, the nickel salt, and the manganese salt in deionized water and adding dropwise to the ionic liquid further comprises:
lithium salt, M source compound, nickel salt and manganese salt are configured according to the molar ratio of Li to M to Ni to Mn (0.95-1.15) to x (0.4-0.5) to (1.4-1.5), wherein x is more than 0 and less than or equal to 0.2.
3. The method according to claim 1, wherein the ionic liquid comprises any one of diethanolamine lactate, diethanolamine formate, ethanolamine lactate, diethanolamine acetate, and 1-ethyl-3-methylimidazolium tetrafluoroborate.
4. The method according to claim 1, wherein the temperature of the pre-decomposition treatment is 400 ℃ to 500 ℃ and the time of the pre-decomposition treatment is 6h to 8 h.
5. The method according to claim 1, wherein the sintering temperature is 800 ℃ to 900 ℃ and the sintering time is 10h to 12 h.
6. The method of any one of claims 1-5, wherein the lithium salt comprises at least one of lithium acetate, lithium oxalate, lithium carbonate, and lithium nitrate; the nickel salt comprises at least one of nickel acetate, nickel oxalate, nickel sulfate and nickel nitrate; the manganese salt comprises at least one of manganese acetate, manganese oxalate, manganese sulfate and manganese nitrate.
7. The method according to any one of claims 1 to 5, wherein the carbon source compound comprises at least one of sucrose, glucose, pitch, graphene, and acetylene black.
8. A high-voltage lithium nickel manganese oxide positive electrode composite material is characterized by being prepared by the preparation method of the high-voltage lithium nickel manganese oxide positive electrode composite material according to any one of claims 1 to 7.
9. A lithium ion battery comprising a positive electrode, wherein the positive electrode comprises the high voltage lithium nickel manganese oxide positive electrode composite of claim 8.
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| CN103094552A (en) * | 2012-10-12 | 2013-05-08 | 合肥国轩高科动力能源股份公司 | Surface coating method of 5V lithium ion battery positive pole material LiNi0.5-xMn1.5MxO4 |
| CN103700838A (en) * | 2013-12-24 | 2014-04-02 | 安徽理工大学 | Preparation method and product of ionic double-doped lithium nickel manganese oxide material, and lithium ion battery |
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| CN103094552A (en) * | 2012-10-12 | 2013-05-08 | 合肥国轩高科动力能源股份公司 | Surface coating method of 5V lithium ion battery positive pole material LiNi0.5-xMn1.5MxO4 |
| CN103700838A (en) * | 2013-12-24 | 2014-04-02 | 安徽理工大学 | Preparation method and product of ionic double-doped lithium nickel manganese oxide material, and lithium ion battery |
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