CN113675396B - Composite lithium cobalt oxide positive electrode material, preparation method and lithium ion battery - Google Patents
Composite lithium cobalt oxide positive electrode material, preparation method and lithium ion battery Download PDFInfo
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- CN113675396B CN113675396B CN202110975252.6A CN202110975252A CN113675396B CN 113675396 B CN113675396 B CN 113675396B CN 202110975252 A CN202110975252 A CN 202110975252A CN 113675396 B CN113675396 B CN 113675396B
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- 229910000625 lithium cobalt oxide Inorganic materials 0.000 title claims abstract description 69
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000002245 particle Substances 0.000 claims abstract description 69
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000010405 anode material Substances 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims description 6
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 235000011054 acetic acid Nutrition 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
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 3
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims 1
- 229910000428 cobalt oxide Inorganic materials 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 238000005056 compaction Methods 0.000 abstract description 7
- 238000005096 rolling process Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 239000011163 secondary particle Substances 0.000 description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000010416 ion conductor Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 229910018871 CoO 2 Inorganic materials 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003571 electronic cigarette Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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 provides a composite lithium cobalt oxide positive electrode material, which comprises large-particle lithium cobalt oxide and small-particle lithium cobalt oxide crystals composited on the surfaces and gaps of the large particles. The invention provides large particle LiCoO 2 The positive electrode material forms a support structure of the composite lithium cobaltate which bears stress during rolling, and has excellent electronic conductivity. Small particle LiCoO 2 The positive electrode material is distributed in the particle LiCoO 2 Gaps or surfaces can provide a large amount of lithium ions when the material is rapidly charged and discharged. The structure effectively integrates the advantages of high electron conductivity, high compaction density, excellent multiplying power performance and high lithium ion mobility of the large-particle lithium cobalt oxide anode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite lithium cobaltate positive electrode material, a preparation method and a lithium ion battery.
Background
Along with the development of the application field of the lithium ion battery, the requirement on the energy density of the battery is higher and higher, and the positive electrode materials of the lithium ion battery which are commercialized and mature at present are lithium cobaltate, lithium manganate, ternary materials and lithium iron phosphate. The lithium cobaltate has high specific capacity and high compaction density, is very suitable for being applied to the field with higher requirements on the volume energy density and the multiplying power performance of the battery, such as electronic products of electronic cigarettes, electric tools, unmanned planes, aviation models, navigation models and the like, but the improvement of the multiplying power performance of the lithium cobaltate becomes a critical problem to be solved urgently. In addition, in the preparation of the lithium ion battery cathode material, technicians usually add excessive lithium-containing compounds to avoid lithium-deficient crystal defects of the material due to the volatility of the lithium-containing compounds at high temperatureAnd (5) sinking. However, excessive amounts of lithium-containing compounds cannot be completely volatilized, resulting in the occurrence of multi-lithium crystal defects Li in the material 1+δ CoO 2 Which can affect the recycling properties of the material.
For example, chinese patent publication No. CN103647074B discloses a high-rate lithium cobaltate and a preparation method thereof, in which cobalt raw material and doping substances (Mg, al, ti, zr, nb oxide or organic matter) are added in proportion, and then dispersed uniformly in an organic dispersion solution, and then lithium carbonate is added for mixing, drying and high-temperature sintering, and then high-speed rotary equipment is used for powdering treatment to obtain lithium cobaltate with good rate performance. The lithium cobaltate prepared by the method is agglomerated into secondary particle size D by primary particles with the primary particle size of 1-3 mu m 50 Lithium cobaltate of 2-7 μm. The secondary particles formed by the agglomeration have no supporting structure, larger pores exist among the primary particles, and the secondary particles are easy to break under certain pressure, so that the compaction density of the pole piece is reduced, and the cycle performance of the battery is reduced. The Chinese patent publication No. CN105870441B discloses a high-magnification lithium cobalt oxide positive electrode material and a preparation method thereof, wherein lithium cobalt oxide is prepared by mixing primary particles with a fast ion conductor Li α M’ γ O β (element M' is Ti, zr, Y, V, nb, mo, sn, in, la, W) fused together and formed into secondary particles; and lithium cobaltate is embedded in the multichannel network of fast ionic conductors. By the method, the lithium ion conductivity of the lithium cobalt oxide anode material is promoted, and the rate capability of the material is improved. The interface with a plurality of phase structures on the surface of the lithium cobaltate prepared by the method and the electronic conductivity of the fast ion conductor network are poor, and although the lithium ion conductivity is improved, the electronic conductivity is reduced due to the existence of the interface and the shielding of the fast ion conductor network, and the improvement effect on the material multiplying power performance is limited.
The patent introduces other metal element impurities, has complex process, consumes very large electric power and water resources, and cannot improve the multiplying power performance and the cycle performance of lithium cobaltate at the same time.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a composite lithium cobalt oxide positive electrode material, a preparation method and a lithium ion battery.
The invention provides a composite lithium cobalt oxide positive electrode material, which comprises large-particle lithium cobalt oxide and small-particle lithium cobalt oxide crystals composited on the surfaces and gaps of the large particles.
Preferably, the particle size of the large-particle lithium cobaltate is 5-30 μm, and the particle size of the small-particle lithium cobaltate crystal is 0.2-2 μm.
The invention also provides a preparation method of the composite lithium cobalt oxide positive electrode material, which comprises the following steps:
a) Mixing cobalt-containing compound and lithium-containing compound, and sintering to obtain LiCoO 2 An intermediate;
b) Introducing acid steam into the LiCoO 2 Intermediate, reacting to obtain reaction product;
c) And (3) carrying out heat treatment on the reaction product to obtain the composite lithium cobalt oxide anode material.
Preferably, in the step a), the cobalt-containing compound is selected from one or more of cobaltosic oxide, cobalt chloride, cobalt carbonate and cobalt hydroxide;
the lithium-containing compound is selected from one or more of lithium carbonate and lithium hydroxide;
the molar ratio of the cobalt-containing compound to the lithium-containing compound is 1: (0.95-1.1).
Preferably, in the step A), the sintering temperature is 750-1000 ℃ and the sintering time is 5-20 h.
Preferably, in step B), the acid vapor contains nitric acid, formic acid, acetic acid, propionic acid, butyric acid, CO 2 And water vapor of one or more of nitrogen dioxide.
Preferably, in the step B), the pH value of the acid steam is 3-6.9; the temperature of the acid steam is 60-250 ℃, and the time for introducing the acid steam is 0.1-2 h.
Preferably, in the step C), the temperature of the heat treatment is 850-1200 ℃, and the time of the heat treatment is 5-20 h.
The invention also provides a lithium ion battery, which comprises the composite lithium cobalt oxide positive electrode material or the composite lithium cobalt oxide positive electrode material prepared by the preparation method.
Compared with the prior art, the invention provides a composite lithium cobalt oxide positive electrode material, which comprises large-particle lithium cobalt oxide and small-particle lithium cobalt oxide crystals composited on the surfaces and gaps of the large particles. The invention provides large particle LiCoO 2 The positive electrode material forms a support structure of the composite lithium cobaltate which bears stress during rolling, and has excellent electronic conductivity. Small particle LiCoO 2 The positive electrode material is distributed in the particle LiCoO 2 Gaps or surfaces can provide a large amount of lithium ions when the material is rapidly charged and discharged. The structure effectively integrates the advantages of high electron conductivity, high compaction density, excellent multiplying power performance and high lithium ion mobility of the large-particle lithium cobalt oxide anode material.
The invention also provides a preparation method of the composite lithium cobalt oxide positive electrode material, which comprises the following steps: a) Mixing cobalt-containing compound and lithium-containing compound, and sintering to obtain LiCoO 2 An intermediate; b) Introducing acid steam into the LiCoO 2 Intermediate, reacting to obtain reaction product; c) And (3) carrying out heat treatment on the reaction product to obtain the composite lithium cobalt oxide anode material.
In the present invention, li having crystal defects is subjected to acid vapor 1+δ CoO 2 The dissolution and recrystallization can keep the basic structure of large-particle lithium cobalt oxide, and small-particle lithium cobalt oxide crystals grow in gaps or surfaces of the large-particle lithium cobalt oxide. Large particle LiCoO 2 The positive electrode material forms a support structure of the composite lithium cobaltate which bears stress during rolling, and has excellent electronic conductivity. Small particle LiCoO 2 The positive electrode material is distributed in the particle LiCoO 2 Gaps or surfaces can provide a large amount of lithium ions when the material is rapidly charged and discharged. The structure effectively integrates the advantages of high electron conductivity, high compaction density, excellent multiplying power performance and high lithium ion mobility of the large-particle lithium cobalt oxide anode material.
The preparation method of the composite lithium cobalt oxide anode material does not introduce other metal element impurities, has very small consumption of electric power and water resources, simple process and lower preparation cost, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an electron scan photograph of a composite lithium cobalt oxide positive electrode material prepared in example 1 of the present invention;
FIG. 2 is an electron scan photograph of a lithium cobaltate cathode material prepared in comparative example 1 of the present invention;
FIG. 3 is a graph showing comparison of cycle performance curves of lithium ion batteries fabricated using example 1 of the present invention and comparative example 1;
fig. 4 is a graph showing comparison of the rate performance curves of lithium ion batteries fabricated using example 1 of the present invention and comparative example 1.
Detailed Description
The invention provides a composite lithium cobalt oxide positive electrode material, which comprises large-particle lithium cobalt oxide and small-particle lithium cobalt oxide crystals composited on the surfaces and gaps of the large particles.
Wherein the particle size of the large-particle lithium cobaltate is 5-30 μm, preferably 5, 10, 15, 20, 25, 30, or any value between 5-30 μm, and the particle size of the small-particle lithium cobaltate crystals is 0.2-2 μm, preferably any value between 0.5, 1.0, 1.5, 2, or 0.2-2 μm.
The mass ratio of the large-particle lithium cobalt oxide to the small-particle lithium cobalt oxide crystals is 1: (0.001-0.1).
The invention also provides a preparation method of the composite lithium cobalt oxide positive electrode material, which comprises the following steps:
a) Mixing cobalt-containing compound and lithium-containing compound, and sintering to obtain LiCoO 2 An intermediate;
b) Introducing acid steam into the LiCoO 2 Intermediate, reacting to obtain reaction product;
c) And (3) carrying out heat treatment on the reaction product to obtain the composite lithium cobalt oxide anode material.
Firstly, mixing cobalt-containing compound and lithium-containing compound, then sintering so as to obtain LiCoO 2 An intermediate. Wherein the cobalt-containing compoundOne or more selected from cobaltosic oxide, cobalt chloride, cobalt carbonate and cobalt hydroxide;
the lithium-containing compound is selected from one or more of lithium carbonate and lithium hydroxide;
the molar ratio of the cobalt-containing compound to the lithium-containing compound is 1: (0.95-1.1).
The sintering temperature is 750-1000 ℃, preferably 750, 800, 850, 900, 950, 1000, or any value between 750-1000 ℃, for a time of 5-20 hours, preferably 5, 10, 15, 20, or any value between 5-20 hours.
Then, acid steam is introduced into the LiCoO 2 And (3) reacting the intermediate to obtain a reaction product.
The acid vapor contains nitric acid, formic acid, acetic acid, propionic acid, butyric acid and CO 2 And water vapor of one or more of nitrogen dioxide. Preferably, the acid steam contains nitric acid, acetic acid and CO 2 And water vapor of one or more of nitrogen dioxide. More preferably, the acid vapor is a vapor containing nitric acid, acetic acid and CO 2 Water vapor of one or more of the following.
The pH value of the acid steam is 3-6.9, preferably 3, 4, 5, 6, 6.5, 6.9, or any value between 3 and 6.9; the temperature of the acid steam is 60-250 ℃, preferably 60, 80, 90, 100, 150, 200, 250, or any value between 60-250 ℃, and the time of introducing the acid steam is 0.1-2 h, preferably 0.1, 0.5, 1.0, 1.5, 2, or any value between 0.1-2 h.
And then, carrying out heat treatment on the reaction product to obtain the composite lithium cobalt oxide positive electrode material.
The temperature of the heat treatment is 850-1200 ℃, preferably 850, 900, 1000, 1100, 1200, or any value between 850-1200 ℃; the time of the heat treatment is 5 to 20 hours, preferably 5, 10, 15, 20, or any value between 5 and 20 hours.
The invention also provides a lithium ion battery, which comprises the composite lithium cobalt oxide anode material.
The invention provides a composite cobaltThe lithium acid anode material comprises large-particle lithium cobalt oxide and small-particle lithium cobalt oxide crystals compounded on the surfaces and gaps of the large particles. The invention provides large particle LiCoO 2 The positive electrode material forms a support structure of the composite lithium cobaltate which bears stress during rolling, and has excellent electronic conductivity. Small particle LiCoO 2 The positive electrode material is distributed in the particle LiCoO 2 Gaps or surfaces can provide a large amount of lithium ions when the material is rapidly charged and discharged. The structure effectively integrates the advantages of high electron conductivity, high compaction density, excellent multiplying power performance and high lithium ion mobility of the large-particle lithium cobalt oxide anode material.
The invention also provides a preparation method of the composite lithium cobalt oxide positive electrode material, which comprises the following steps: a) Mixing cobalt-containing compound and lithium-containing compound, and sintering to obtain LiCoO 2 An intermediate; b) Introducing acid steam into the LiCoO 2 Intermediate, reacting to obtain reaction product; c) And (3) carrying out heat treatment on the reaction product to obtain the composite lithium cobalt oxide anode material.
In the present invention, li having crystal defects is subjected to acid vapor 1+δ CoO 2 The dissolution and recrystallization can keep the basic structure of large-particle lithium cobalt oxide, and small-particle lithium cobalt oxide crystals grow in gaps or surfaces of the large-particle lithium cobalt oxide. Large particle LiCoO 2 The positive electrode material forms a support structure of the composite lithium cobaltate which bears stress during rolling, and has excellent electronic conductivity. Small particle LiCoO 2 The positive electrode material is distributed in the particle LiCoO 2 Gaps or surfaces can provide a large amount of lithium ions when the material is rapidly charged and discharged. The structure effectively integrates the advantages of high electron conductivity, high compaction density, excellent multiplying power performance and high lithium ion mobility of the large-particle lithium cobalt oxide anode material.
The preparation method of the composite lithium cobalt oxide anode material does not introduce other metal element impurities, has very small consumption of electric power and water resources, simple process and lower preparation cost, and is suitable for large-scale industrial production.
In order to further understand the present invention, the composite lithium cobaltate positive electrode material, the preparation method and the lithium ion battery provided by the present invention are described below with reference to examples, and the scope of protection of the present invention is not limited by the following examples.
Example 1
Co is to be 3 O 4 With Li 2 CO 3 According to the mole ratio of 1: mixing 0.55, sintering at 970 deg.C for 12 hr, and naturally cooling to obtain LiCoO 2 An intermediate;
introducing nitric acid vapor with pH value of 4 and temperature of 200 ℃ into the LiCoO 2 Intermediate, reaction time is 0.5h;
and sintering the product obtained in the last step at 1000 ℃ for 16 hours, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
The morphology of the composite lithium cobalt oxide positive electrode material prepared in example 1 was characterized by using an electron scanning electron microscope, and an electron scanning photograph as shown in fig. 1 was obtained. From fig. 1, it can be observed that the lithium cobaltate positive electrode material has a composite structure morphology, and the secondary particles with the particle size of about 16 μm to 22 μm comprise particles a: small particle LiCoO 2 The particle size of the positive electrode material is about 0.8-1.5 mu m; particle b: large particle LiCoO 2 Positive electrode material, lithium cobaltate particles with the particle size of 6-8 mu m; particles a are embedded in the gaps between particles b.
The composite lithium cobaltate positive electrode material is prepared into a battery, and the specific method is as follows:
the positive electrode material is prepared into a lithium ion battery, and the specific method comprises the following steps: 9g of the composite lithium ion battery positive electrode material obtained in the example 1, 0.5g of acetylene black, 0.5g of polyvinylidene fluoride and 20g of N-methyl pyrrolidone are mixed at normal temperature and normal pressure to form slurry, and the slurry is uniformly coated on the surface of an aluminum foil to prepare the pole piece.
Drying the pole piece obtained in the last step at 80 ℃, compacting, and cutting into 1.32cm 2 As positive electrode, pure lithium sheet as negative electrode, and 1mol/L of solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) of LiPF6 as electrolyte, wherein the volume ratio of EC to DMC is 1:1, then assembled into a lithium ion battery in a glove box filled with argon.
Comparative example 1
Co is to be 3 O 4 With Li 2 CO 3 Uniformly mixing according to a molar ratio of 1:0.5, sintering at 1000 ℃ for 16 hours, and naturally cooling to obtain LiCoO 2 A positive electrode material;
the morphology of the lithium cobalt oxide positive electrode material prepared in comparative example 1 was characterized by using an electron scanning electron microscope, and an electron scanning photograph as shown in fig. 2 was obtained. From fig. 2, it can be observed that the lithium cobaltate positive electrode material has a single crystal morphology, and that the particle size is about 8-12 μm.
The above positive electrode material was prepared as a battery by the method described in example 1.
The performance of the obtained batteries of example 1 and comparative example 1 was tested, and the results are shown in fig. 3 and 4, and fig. 4 is a cut-out view of the discharge portion of the battery at a rate of 50 weeks before fig. 3. Fig. 3 is a graph showing comparison of cycle performance curves of lithium ion batteries fabricated using example 1 of the present invention and comparative example 1. As can be seen from fig. 3 and 4, the battery prepared in example 1 has a specific 0.1C discharge capacity of 162.3mAh/g, a specific 0.2C discharge capacity of 158.6mAh/g, a specific 2C discharge capacity of 151.8mAh/g, a specific 3C discharge capacity of 140.6mAh/g, a specific 5C discharge capacity of 130.7mAh/g, and a retention rate of 5C/0.1C discharge capacity of 80.5%; the specific discharge capacity at 1.0C was 156.9mAh/g, at 152.9mAh/g after 200 weeks of 1.0C cycle, and at 97.4% after 200 weeks of cycle. Comparative example 1 produced a battery with a specific discharge capacity of 158.5mAh/g at 0.2C, 156.6mAh/g at 2C, 148.1mAh/g at 3C, 130.6mAh/g at 5C, 111.7mAh/g at 5C, and a discharge capacity retention of 70.5% at 5C/0.1C. The specific discharge capacity at 1.0C was 155.2mAh/g, the specific discharge capacity at 1.0C after 200 weeks was 137.9mAh/g, and the capacity retention after 200 weeks of the cycle was 88.8%. The rate performance of example 1 was better and the cycle performance was better.
Example 2
Co is to be 3 O 4 With Li 2 CO 3 According to the mole ratio of 1: mixing 0.52 uniformly, sintering at 950 ℃ for 10 hours, and naturally cooling to obtain LiCoO 2 An intermediate;
CO with pH value of 6 and temperature of 150 DEG C 2 Steam ventilationInto the LiCoO 2 Intermediate, reaction time is 0.4h;
and sintering the product obtained in the last step for 18 hours at 980 ℃, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 3
CoCO is to 3 The molar ratio of the catalyst to LiOH is 1:1.06 is evenly mixed, sintered for 12 hours at 850 ℃, and naturally cooled to obtain LiCoO 2 An intermediate;
introducing acetic acid vapor with pH value of 5 and temperature of 220 ℃ into the LiCoO 2 Intermediate, reaction time is 0.8h;
and sintering the product obtained in the last step at 950 ℃ for 12 hours, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 4
CoCO is to 3 With Li 2 CO 3 According to the mole ratio of 1: mixing 0.53 uniformly, sintering at 800 deg.C for 8 hr, naturally cooling to obtain LiCoO 2 An intermediate;
introducing nitric acid vapor with pH value of 3 and temperature of 120 ℃ into the LiCoO 2 Intermediate, reaction time is 0.2h;
and sintering the product of the last step at 1050 ℃ for 10 hours, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 5
Co is to be 3 O 4 With Li 2 CO 3 According to the mole ratio of 1: mixing 0.51, sintering at 1000deg.C for 8 hr, and naturally cooling to obtain LiCoO 2 An intermediate;
introducing formic acid vapor with pH value of 5.5 and temperature of 90 ℃ into the LiCoO 2 Intermediate, reaction time is 1.2h;
and sintering the product obtained in the last step for 20 hours at 950 ℃, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 6
Co is to be 3 O 4 The molar ratio of the catalyst to LiOH is 1:1.05, sintering at 900 deg.C for 10 hr, and naturally cooling to obtain LiCoO 2 An intermediate;
CO with pH value of 6.5 and temperature of 220 DEG C 2 Steam is introduced into the LiCoO 2 Intermediate, reaction time is 1h;
and sintering the product obtained in the last step for 18 hours at 980 ℃, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 7
Co (OH) 3 With Li 2 CO 3 According to the mole ratio of 1: mixing 0.52 uniformly, sintering at 900 deg.C for 18 hr, naturally cooling to obtain LiCoO 2 An intermediate;
introducing propionic acid vapor with pH value of 4.8 and temperature of 100deg.C into LiCoO 2 Intermediate, the reaction time is 2h;
and sintering the product obtained in the last step at 990 ℃ for 14 hours, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 8
Co is to be 3 O 4 With Li 2 CO 3 According to the mole ratio of 1: mixing 0.53 uniformly, sintering at 920 deg.C for 10 hr, naturally cooling to obtain LiCoO 2 An intermediate;
introducing nitrogen dioxide steam with pH value of 6 and temperature of 150 ℃ into the LiCoO 2 Intermediate, the reaction time is 2h;
and sintering the product obtained in the last step at 1000 ℃ for 16 hours, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 9
Co is to be 3 O 4 With Li 2 CO 3 According to the mole ratio of 1: mixing 0.55, sintering at 970 deg.C for 12 hr, and naturally cooling to obtain LiCoO 2 An intermediate;
introducing butyric acid vapor with pH value of 5.5 and temperature of 95 ℃ into the LiCoO 2 Intermediate, reaction time is 0.3h;
and carrying out heat treatment on the product obtained in the last step at 1020 ℃ for 15 hours, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
Example 10
CoCO is to 3 The molar ratio of the catalyst to LiOH is 1:1.08, sintering at 910 deg.C for 12 hr, and naturally cooling to obtain LiCoO 2 An intermediate;
introducing acid acetate vapor with pH value of 5 and temperature of 100 ℃ into the LiCoO 2 Intermediate, reaction time is 0.2h;
and carrying out heat treatment on the product obtained in the last step at 980 ℃ for 18 hours, and naturally cooling to obtain the composite lithium cobalt oxide anode material.
The rate performance and cycle performance of examples 1 to 10 and comparative example 1 were tested, and the structures are shown in the following table:
from the experimental data, examples 1 to 10 provided by the present invention are superior to comparative example 1 in both rate performance and cycle performance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The composite lithium cobalt oxide positive electrode material is characterized by comprising large-particle lithium cobalt oxide and small-particle lithium cobalt oxide crystals which are composited on the surfaces and gaps of the large particles;
the preparation method of the composite lithium cobalt oxide positive electrode material comprises the following steps:
a) Mixing cobalt-containing compound and lithium-containing compound, and sintering to obtain LiCoO 2 An intermediate;
b) Introducing acid steam into the LiCoO 2 Intermediate, reacting to obtain reaction product;
the acid vapor contains nitric acid, formic acid, acetic acid, propionic acid, butyric acid and CO 2 And water vapor of one or more of nitrogen dioxide; the pH value of the acid steam is 3-6.9; the temperature of the acid steam is 60-250 ℃, and the acid steam is introducedThe time for entering the acid steam is 0.1-2 h;
c) After heat treatment of the reaction product, a composite lithium cobalt oxide anode material is obtained;
the temperature of the heat treatment is 850-1200 ℃, and the time of the heat treatment is 5-20 h.
2. The composite lithium cobaltate cathode material according to claim 1, wherein the particle size of the large-particle lithium cobaltate is 5-30 μm, and the particle size of the small-particle lithium cobaltate crystal is 0.2-2 μm.
3. A method for preparing the composite lithium cobalt oxide positive electrode material according to any one of claims 1 to 2, comprising the steps of:
a) Mixing cobalt-containing compound and lithium-containing compound, and sintering to obtain LiCoO 2 An intermediate;
b) Introducing acid steam into the LiCoO 2 Intermediate, reacting to obtain reaction product;
the acid vapor contains nitric acid, formic acid, acetic acid, propionic acid, butyric acid and CO 2 And water vapor of one or more of nitrogen dioxide; the pH value of the acid steam is 3-6.9; the temperature of the acid steam is 60-250 ℃, and the time for introducing the acid steam is 0.1-2 h;
c) After heat treatment of the reaction product, a composite lithium cobalt oxide anode material is obtained;
the temperature of the heat treatment is 850-1200 ℃, and the time of the heat treatment is 5-20 h.
4. The method according to claim 3, wherein in the step A), the cobalt-containing compound is one or more selected from the group consisting of tricobalt tetraoxide, cobalt oxide, cobalt chloride, cobalt carbonate and cobalt hydroxide;
the lithium-containing compound is selected from one or more of lithium carbonate and lithium hydroxide;
the molar ratio of the cobalt-containing compound to the lithium-containing compound is 1: (0.95-1.1).
5. The method according to claim 3, wherein in the step A), the sintering temperature is 750-1000 ℃ and the sintering time is 5-20 hours.
6. A lithium ion battery, characterized by comprising the composite lithium cobalt oxide positive electrode material according to any one of claims 1 to 2 or the composite lithium cobalt oxide positive electrode material prepared by the preparation method according to any one of claims 3 to 5.
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