CN114512662A - Lithium ion battery anode material and preparation method thereof, and lithium ion battery - Google Patents
Lithium ion battery anode material and preparation method thereof, and lithium ion battery Download PDFInfo
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- CN114512662A CN114512662A CN202210199214.0A CN202210199214A CN114512662A CN 114512662 A CN114512662 A CN 114512662A CN 202210199214 A CN202210199214 A CN 202210199214A CN 114512662 A CN114512662 A CN 114512662A
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- ion battery
- lithium ion
- salt
- cobalt
- nickel
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010405 anode material Substances 0.000 title claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 239000007774 positive electrode material Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000011812 mixed powder Substances 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
- 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
- 238000005245 sintering Methods 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 6
- 239000011163 secondary particle Substances 0.000 abstract description 4
- 239000002135 nanosheet Substances 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 9
- 229910013716 LiNi Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 4
- 235000019799 monosodium phosphate Nutrition 0.000 description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 3
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 229910021385 hard carbon Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Complex oxides containing cobalt and at least one other metal element
- C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
- C01G51/44—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/50—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2 containing manganese of the type (MnO2)n-, e.g. Li(CoxMn1-x)O2 or Li(MyCoxMn1-x-y)O2
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- 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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a lithium ion battery anode material, a preparation method thereof and a lithium ion battery, wherein nickel salt, cobalt salt and manganese salt are dissolved in a mixed solvent of glycerol and isopropanol, the pH value of the mixed solvent is adjusted, a microwave hydrothermal method is adopted to prepare a precursor of secondary particles consisting of a plurality of tiny nanosheets, the precursor is pre-sintered in an air environment and then mixed with lithium salt, and the mixture is calcined step by step in an oxygen atmosphere to prepare the lithium ion battery anode material with the median particle size of 3.5-6.0 microns and the micro morphology of small-particle polycrystalPolar material Li (Ni)xCoyMnz)O2The lithium ion battery prepared by using the material as a positive electrode active substance can be charged and discharged at a high rate, and shows excellent rate performance.
Description
Technical Field
The invention belongs to the technical field of preparation of new energy lithium ion battery anode materials, and particularly relates to a lithium ion battery anode material, a preparation method thereof and a lithium ion battery.
Background
The realization of the ultra-high voltage transmission technology and the proposal of 'carbon peak reaching' and 'carbon neutralization' further promote the development of replacing traditional thermal power by clean energy such as photoelectricity, wind power and the like, thereby increasing the demand of people on energy storage devices. Among many energy storage devices, lithium ion batteries have been widely used in the fields of energy storage, electric vehicles, etc. due to their long life, high specific capacity, and small size. However, it is desirable that the lithium ion battery can be charged rapidly at a higher rate to meet the demand of the power source.
The lithium ion battery mainly depends on the electronic conduction of an external circuit, and the insertion/extraction and diffusion of lithium ions in the battery between positive and negative electrode materials to realize the conversion of electric energy and chemical energy. The literature shows that the diffusion coefficients of lithium ions in liquid electrolytes and solid-phase materials are 10 respectively-7～10-5cm2s-1And 10-12～10-8cm2s-1. Therefore, the diffusion of lithium ions inside the electrode sheet, especially the positive electrode material, is a limiting step of the electrochemical reaction of the lithium ion battery.
On the other hand, if the particle size of the positive electrode material is too large, the diffusion path of lithium ions in the material becomes long, increasing the time for lithium ion intercalation/deintercalation, and further affecting the rate capability of the lithium ion battery.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lithium ion battery cathode material and a preparation method thereof, the lithium ion battery cathode material with a median particle size of 3.5-6.0 microns and small-particle polycrystal microcosmic appearance can be prepared by the method, and the preparation method is simple and environment-friendly.
The invention also provides a lithium ion battery, wherein the anode of the lithium ion battery is prepared by taking the lithium ion battery anode material as an active substance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a lithium ion battery positive electrode material comprises the following steps:
(1) dissolving nickel salt, cobalt salt and manganese salt in a mixed solvent of glycerol and isopropanol to obtain a mixed solution, and then adjusting the pH of the mixed solution to 10.0-12.0;
(2) transferring the mixed solution obtained in the step (1) into a microwave reaction kettle, carrying out microwave hydrothermal reaction at 150-200 ℃, after the reaction is finished, cooling the reaction solution, and carrying out suction filtration, washing and drying to obtain a precursor;
(3) presintering the precursor in an air environment to obtain nickel-cobalt-manganese oxide;
(4) and (3) uniformly mixing the nickel-cobalt-manganese oxide and the lithium salt to obtain mixed powder, and calcining step by step in an oxygen atmosphere to obtain the lithium ion battery anode material.
In the step (1), the molar ratio of the nickel salt, the cobalt salt and the manganese salt is any molar ratio; the volume ratio of the glycerol to the isopropanol is 1: 1-5; the concentration of the metal ions in the mixed solution is 1.5-2.5 mol/L.
In the step (1), the pH is adjusted by using a buffer solution of sodium dihydrogen phosphate and sodium hydroxide with the pH of 10-12.
In the step (2), the microwave hydrothermal reaction time is 3-5 h.
In the step (3), the presintering conditions in the air are as follows: pre-sintering at 240-260 ℃ for 1-2 h.
In the step (4), the molar ratio of the nickel-cobalt-manganese oxide to the lithium salt is 1: 1-1.06.
In the step (4), the calcining conditions are as follows: calcining at 450-550 ℃ for 3.5-4.5 h, and then heating to 700-1000 ℃ and preserving heat for 10-14 h.
The rate of temperature rise is 2.5-3.5 ℃/min.
The nickel salt is any one or more of nickel chloride, nickel sulfate, nickel nitrate and nickel acetate;
the cobalt salt is any one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate;
the manganese salt is any one or more of manganese chloride, manganese sulfate, manganese nitrate and manganese acetate;
the lithium salt is any one or more of lithium carbonate and lithium hydroxide.
The invention also provides the lithium ion battery anode material prepared by the preparation method, and the lithium ion battery anode material is Li (Ni)xCoyMnz)O2Wherein x, y and z are respectively the molar ratio of nickel salt, cobalt salt and manganese salt in the raw materials in the total transition metal salt, x + y + z is 1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, the median particle size is 3.5-6.0 micrometers, and the composite material is in the micro-morphology of small-particle polycrystals.
The invention also provides a lithium ion battery, and the anode of the lithium ion battery is prepared by taking the lithium ion battery anode material as an active substance.
Firstly, dissolving nickel salt, cobalt salt and manganese salt in a mixed solvent of glycerol and isopropanol, adjusting the pH value of the mixed solvent, preparing a precursor of secondary particles consisting of a plurality of tiny nanosheets by adopting a microwave hydrothermal method, wherein the particle size of the precursor is 4-5 microns, then uniformly mixing the precursor and a lithium salt solid phase, and preparing a lithium ion battery anode material Li (Ni) with a median particle size of 3.5-6.0 microns and a small-particle polycrystalline micro-morphology by adopting a high-temperature solid phase methodxCoyMnz)O2The lithium ion battery anode prepared by using the material as an active substance is used as the anode of the lithium ion battery, so that the rate capability of the lithium ion battery can be improved.
Drawings
FIG. 1 is an SEM image of the precursor prepared in example 1;
fig. 2 is an SEM image of the positive electrode material for a lithium ion battery prepared in example 1;
FIG. 3 is a particle size distribution diagram of the lithium ion battery positive electrode material prepared in example 1;
fig. 4 is an XRD pattern of the lithium ion battery cathode material prepared in example 1;
fig. 5 is an SEM image of the lithium ion battery positive electrode material prepared in example 2;
fig. 6 is a particle size distribution diagram of the lithium ion battery positive electrode material prepared in example 2;
fig. 7 is an XRD pattern of the lithium ion battery cathode material prepared in example 2;
fig. 8 is an SEM image of the lithium ion battery positive electrode material prepared in example 3;
fig. 9 is a particle size distribution diagram of the lithium ion battery positive electrode material prepared in example 3;
fig. 10 is an XRD pattern of the lithium ion battery cathode material prepared in example 3;
fig. 11 is an XRD pattern of the lithium ion battery positive electrode material prepared in the comparative example;
fig. 12 is a graph of rate performance of each lithium ion battery in an application example.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Lithium ion battery anode material LiNi1/3Co1/3Mn1/3O2The preparation method comprises the following steps:
(1) dissolving nickel sulfate, cobalt sulfate and manganese sulfate in a molar ratio of Ni to Co to Mn of 1:1:1 in 1L of mixed organic solvent consisting of glycerol and isopropanol in a volume ratio of 1:5 to obtain a mixed solution, wherein the concentration of metal ions in the mixed solution is 2mol/L, and uniformly stirring to obtain a transparent solution;
(2) adding a buffer solution of sodium dihydrogen phosphate and sodium hydroxide into the transparent solution obtained in the step (1) while stirring to adjust the pH of the transparent solution to 10.5, so as to obtain a suspension;
(3) transferring the suspension obtained in the step (2) into a microwave reaction kettle, slowly stirring, heating to 150 ℃, and carrying out microwave hydrothermal reaction for 4.5 hours;
(4) after the reaction in the step (3) is finished, cooling the solution to room temperature, carrying out vacuum filtration on the solution to obtain precipitated powder, washing the precipitated powder with deionized water, and drying the washed precipitated powder in a 60 ℃ drying oven for 12 hours to obtain a precursor of the positive electrode material, wherein an SEM image of the precursor is shown in FIG. 1;
(5) presintering the precursor material obtained in the step (4) in air at 250 ℃ for 1h to obtain the oxide Ni of nickel, cobalt and manganese1/3Co1/3Mn1/3O；
(6) Uniformly mixing the nickel-cobalt-manganese oxide obtained in the step (5) with lithium carbonate in a solid phase manner according to a molar ratio of 1:1.03 to obtain a powder mixture;
(7) calcining the powder mixture obtained in the step (6) in pure oxygen atmosphere at 500 ℃ for 4h, then heating to 1000 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 12h, and cooling the furnace temperature to obtain LiNi1/3Co1/3Mn1/3O2The positive electrode material has an SEM image shown in FIG. 2, a particle size distribution diagram shown in FIG. 3, and an XRD image shown in FIG. 4.
As can be seen from fig. 1, the morphology of the precursor of the positive electrode material prepared in this embodiment is a secondary particle composed of a plurality of tiny nanosheets, and the particle size of the secondary particle is about 4-5 μm. The microsheet may develop into primary particles during subsequent calcination.
As can be seen from FIG. 2, LiNi prepared in this example1/3Co1/3Mn1/3O2The micro appearance of the anode material is polycrystalline; as can be seen from FIG. 3, LiNi1/3Co1/3Mn1/3O2The median particle size of the positive electrode material is 5.96 microns; the XRD pattern in FIG. 4 shows that the peak intensity ratio of the characteristic peaks (003)/(104) is 1.30 and greater than 1.2, indicating that LiNi is produced1/3Co1/3Mn1/3O2The cathode material has an excellent hexagonal layered crystal structure.
Example 2
Lithium ion battery anode material LiNi0.5Co0.2Mn0.3O2The preparation method comprises the following steps:
(1) dissolving nickel acetate, cobalt chloride and cobalt nitrate into 1L of mixed organic solvent consisting of glycerol and isopropanol in a volume ratio of 1:1 according to a molar ratio of Ni to Co to Mn of 5:2:3 to obtain a mixed solution, wherein the concentration of metal ions in the mixed solution is 2mol/L, and uniformly stirring to obtain a transparent solution;
(2) adding a buffer solution of sodium dihydrogen phosphate and sodium hydroxide into the transparent solution obtained in the step (1) while stirring to adjust the pH of the transparent solution to 11.2, so as to obtain a suspension;
(3) transferring the suspension liquid obtained in the step (2) into a microwave reaction kettle, slowly stirring, heating to 180 ℃, and carrying out microwave hydrothermal reaction for 4.0 h;
(4) after the reaction in the step (3) is finished, cooling the solution to room temperature, carrying out vacuum filtration on the solution to obtain precipitated powder, washing the precipitated powder with ethanol water, and drying the washed precipitated powder in a 60 ℃ drying oven for 12 hours to obtain a precursor of the positive electrode material;
(5) presintering the precursor material obtained in the step (4) in air at 250 ℃ for 1.5h to obtain the oxide Ni of nickel, cobalt and manganese0.5Co0.2Mn0.3O；
(6) Uniformly mixing the nickel-cobalt-manganese oxide obtained in the step (5) with lithium carbonate in a solid phase manner according to a molar ratio of 1:1.04 to obtain a powder mixture;
(7) calcining the powder mixture obtained in the step (6) in pure oxygen atmosphere at 500 ℃ for 4h, then heating to 800 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 12h, and cooling the furnace temperature to obtain LiNi0.5Co0.2Mn0.3O2The ICP test results of the positive electrode materials are shown in table 1, the SEM image is shown in fig. 5, the particle size distribution diagram is shown in fig. 6, and the XRD diagram is shown in fig. 7.
TABLE 1
| Element(s) | wt.％ | at.％ | at.% (normalization) |
| Li | 7.14 | 50.57 | - |
| Ni | 30.22 | 25.31 | 51.20 |
| Co | 12.11 | 10.10 | 20.43 |
| Mn | 15.67 | 14.02 | 28.36 |
As can be seen from FIG. 5, LiNi prepared in this example0.5Co0.2Mn0.3O2The micro appearance of the anode material is polycrystalline; as can be seen from FIG. 6, LiNi0.5Co0.2Mn0.3O2The median particle size of the positive electrode material is 3.58 microns; the XRD pattern in FIG. 7 shows that the peak intensity ratio of the characteristic peaks (003)/(104) is 1.44 and greater than 1.2, indicating that LiNi is produced0.5Co0.2Mn0.3O2The cathode material has an excellent hexagonal layered crystal structure.
Example 3
Lithium ion battery anode material LiNi0.8Co0.1Mn0.1O2The preparation method comprises the following steps:
(1) dissolving nickel nitrate, cobalt nitrate and manganese nitrate into 1L of mixed organic solvent consisting of glycerol and isopropanol in a volume ratio of 1:3 according to a molar ratio of Ni to Co to Mn of 8:1:1 to obtain a mixed solution, wherein the concentration of metal ions in the mixed solution is 2mol/L, and uniformly stirring to obtain a transparent solution;
(2) adding a buffer solution of sodium dihydrogen phosphate and sodium hydroxide into the transparent solution obtained in the step (1) while stirring to adjust the pH of the transparent solution to 11.5 to obtain a suspension;
(3) transferring the suspension obtained in the step (2) into a microwave reaction kettle, slowly stirring, heating to 200 ℃, and carrying out microwave hydrothermal reaction for 3.5 hours;
(4) after the reaction in the step (3) is finished, cooling the solution to room temperature, carrying out vacuum filtration on the solution to obtain precipitated powder, washing the precipitated powder by using a 50% ethanol solution, and drying the washed precipitated powder in a 60 ℃ drying oven for 12 hours to obtain a precursor of the positive electrode material;
(5) presintering the precursor material obtained in the step (4) in air at 250 ℃ for 2h to obtain the oxide Ni of nickel, cobalt and manganese0.8Co0.1Mn0.1O；
(6) Uniformly mixing the nickel-cobalt-manganese oxide obtained in the step (5) with lithium hydroxide according to a molar ratio of 1:1.06 to obtain a powder mixture;
(7) calcining the powder mixture obtained in the step (6) in pure oxygen atmosphere at 500 ℃ for 4h, then heating to 750 ℃ at a heating rate of 3 ℃/min, preserving heat for 12h, and obtaining LiNi after furnace temperature cooling0.8Co0.1Mn0.1O2The positive electrode material is shown in an SEM image in figure 8, a particle size distribution diagram in figure 9 and an XRD image in figure 10.
As can be seen from FIG. 8, LiNi prepared in this example0.8Co0.1Mn0.1O2The micro appearance of the anode material is polycrystalline; as can be seen from FIG. 9, LiNi0.8Co0.1Mn0.1O2The median particle size of the positive electrode material is 4.14 microns; the XRD pattern in FIG. 10 shows that the peak intensity ratio of the characteristic peaks (003)/(104) is 1.44 and greater than 1.2, indicating that LiNi is produced0.8Co0.1Mn0.1O2The cathode material has an excellent hexagonal layered crystal structure.
Comparative example
The procedure is otherwise the same as in example 1, except that the solvents glycerol and isopropanol in step (1) are replaced by equal amounts of deionized water.
LiNi prepared by this comparative example1/3Co1/3Mn1/3O2The XRD pattern of the cathode material is shown in FIG. 11.
As can be seen from fig. 11, the peak intensity ratio of the characteristic peaks (003)/(104) is less than 1.2, indicating that the hexagonal layered crystal structure of the material prepared in the comparative example is not significant and has poor electrochemical properties.
Application example
Respectively taking the positive electrode materials prepared in the embodiments 1, 2, 3 and the comparative example as active substances, uniformly mixing the active substances with PVDF and acetylene black according to the mass ratio of 8:1:1, taking NMP as a dispersing agent, preparing positive electrode slurry, uniformly coating the positive electrode slurry on an aluminum foil current collector, and drying to obtain a positive electrode piece; taking hard carbon as a counter electrode, uniformly mixing the hard carbon, CMC and acetylene black according to the mass ratio of 7:2:1, adding deionized water, pulping, coating and drying to obtain the negative pole piece. The soft package lithium ion battery with the capacity of 1.35Ah is designed and manufactured according to the N/P (the negative electrode capacity/the positive electrode capacity) of 1.12, and the rate performance test is carried out on the soft package lithium ion battery. The test procedure for the rate capability is as follows: the discharge was performed at a rate of 0.5C, 1.0C, 2.0C, 3.0C, 6.0C, 10.0C, 20.0C, and 30.0C, respectively, and the data are shown in table 2 and fig. 12.
TABLE 2
As can be seen from the data in table 1, the positive electrode material prepared by the present invention can still release more than 85% of capacity at a current density of 30.0C, and has excellent rate capability, which indicates that the time for lithium ion intercalation/deintercalation can be shortened by using the positive electrode active material having a smaller median particle size in the preparation of the positive electrode, thereby improving the rate capability of the battery.
The above detailed description of a lithium ion battery positive electrode material, a method of preparing the same, and a lithium ion battery, with reference to the examples, is illustrative and not restrictive, and several examples may be cited within the scope of the present invention, so that variations and modifications may be made without departing from the general inventive concept within the scope of the present invention.
Claims (10)
1. A preparation method of a lithium ion battery positive electrode material is characterized by comprising the following steps:
(1) dissolving nickel salt, cobalt salt and manganese salt in a mixed solvent of glycerol and isopropanol to obtain a mixed solution, and then adjusting the pH of the mixed solution to 10.0-12.0;
(2) transferring the mixed solution obtained in the step (1) into a microwave reaction kettle, carrying out microwave hydrothermal reaction at 150-200 ℃, after the reaction is finished, cooling the reaction solution, carrying out suction filtration, washing and drying to obtain a precursor;
(3) presintering the precursor in an air environment to obtain nickel-cobalt-manganese oxide;
(4) and uniformly mixing the nickel-cobalt-manganese oxide and a lithium salt solid phase to obtain mixed powder, and calcining the mixed powder step by step in an oxygen atmosphere to obtain the lithium ion battery anode material.
2. The preparation method according to claim 1, wherein in the step (1), the molar ratio of the nickel salt, the cobalt salt and the manganese salt is any molar ratio; the volume ratio of the glycerol to the isopropanol is 1: 1-5; the concentration of the metal ions in the mixed solution is 1.5-2.5 mol/L.
3. The preparation method according to claim 1, wherein in the step (2), the microwave hydrothermal reaction is carried out for 3-5 hours.
4. The production method according to claim 1, wherein in the step (3), the conditions for the pre-sintering in air are: pre-sintering at 240-260 ℃ for 1-2 h.
5. The preparation method according to claim 1, wherein in the step (4), the molar ratio of the nickel-cobalt-manganese oxide to the lithium salt is 1: 1-1.06.
6. The method according to claim 1, wherein in the step (4), the calcination is carried out under the following conditions: calcining at 450-550 ℃ for 3.5-4.5 h, and then heating to 700-1000 ℃ and preserving heat for 10-14 h.
7. The method according to claim 6, wherein the temperature is raised at a rate of 2.5 to 3.5 ℃/min.
8. The preparation method according to any one of claims 1 to 7, wherein the nickel salt is any one or more of nickel chloride, nickel sulfate, nickel nitrate and nickel acetate; the cobalt salt is any one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate; the manganese salt is any one or more of manganese chloride, manganese sulfate, manganese nitrate and manganese acetate; the lithium salt is any one or more of lithium carbonate and lithium hydroxide.
9. The lithium ion battery cathode material prepared by the preparation method according to any one of claims 1 to 8, wherein the lithium ion battery cathode material is Li (Ni)xCoyMnz)O2Wherein x + y + z is 1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, the median particle size is 3.5-6.0 micrometers, and the microstructure of small-particle polycrystals is obtained.
10. The lithium ion battery is characterized in that the positive electrode of the lithium ion battery is prepared by using the positive electrode material of the lithium ion battery as claimed in claim 9 as an active material.
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