CN108899537A - lithium ion battery L iNixCoyMnl-x-yO2Preparation method of positive electrode material - Google Patents
lithium ion battery L iNixCoyMnl-x-yO2Preparation method of positive electrode material Download PDFInfo
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- CN108899537A CN108899537A CN201810780096.6A CN201810780096A CN108899537A CN 108899537 A CN108899537 A CN 108899537A CN 201810780096 A CN201810780096 A CN 201810780096A CN 108899537 A CN108899537 A CN 108899537A
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- positive electrode
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims description 8
- 239000007774 positive electrode material Substances 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000004917 carbon fiber Substances 0.000 claims abstract description 13
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 229910013716 LiNi Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 18
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 17
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- 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 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 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 2
- 238000007873 sieving Methods 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 7
- 238000005204 segregation Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 2
- 239000010406 cathode material Substances 0.000 abstract 1
- 239000008139 complexing agent Substances 0.000 abstract 1
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910015216 Ni1/3Co1/3Mn1/3CO3 Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229940117958 vinyl acetate Drugs 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 229910003174 MnOOH Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003835 carbonate co-precipitation Methods 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012546 transfer Methods 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
- H01M4/50—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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
the invention discloses a lithium ion battery L iNixCoyMnl‑x‑yO2Preparation method of cathode material, namely preparation of Ni by adopting solvent/hydrothermal methodxCoyMnl‑x‑yCO3the precursor, wherein urea is used as a complexing agent, can avoid segregation phenomenon of transition metal ions, ensures uniform precipitation of the transition metal ions, and then is fully mixed with a lithium source to prepare the L iNi by a high-temperature solid phase methodxCoyMnl‑x‑yO2And then the conductivity is improved by adding carbon fiber, thereby improvingL iNixCoyMnl‑x‑yO2multiplying power performance of anode material L iNi obtained by the inventionxCoyMnl‑x‑yO2The anode material has higher specific capacity, good high-rate performance and excellent cycle performance, and can be applied to the fields of various portable electronic devices, electric automobiles, energy storage devices and the like.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of lithium ion battery LiNixCoyMnl-x-yO2Positive material
The preparation method of material.
Background technique
Since China is the country of populous nation and energy shortage, per capita resources are few, and Energy situation is very severe, and the energy is asked
Topic is faced with serious challenge.And fossil fuel can release many pernicious gas and dust, it has also become China's ring in burning
One of the source of border pollution.These require that people improve the utilization rate and the reproducible new energy of exploitation cleaning to resource,
Middle lithium ion battery is one of the effective way for realizing the target, to push the application of lithium ion battery commercially.With
Lithium ion battery performance be continuously improved, now have been supplied on the products such as 3C electronic product, electric tool, and in new energy vapour
It is also gradually applied on the fields such as vehicle, energy storage, communication.
LiNixCoyMn1-x-yO2Preparation method mainly has high temperature solid-state method, coprecipitation in material industry.High temperature solid-state method
The advantages that process is simple, easily controllable, and yield is big, at low cost, but its product grain is relatively large, particle diameter distribution consistency is poor
The defects of, affect its performance.Presoma pattern that coprecipitation obtains, granularity are easily controllable, raw material can be equal in atomic level
The features such as even mixing, but its preparation process is relative complex, and procedure parameter is more, is easy to appear loss etc..According to using precipitating reagent
Difference can be divided into hydroxyl coprecipitation, carbonate coprecipitation etc..Wherein due to Mn (OH)2It is easy in aqueous solution
It is oxidized to the MnOOH of trivalent, or even is oxidized to the MnO of tetravalence2, cause presoma component uneven, cause be heat-treated
It obtains forming miscellaneous phase in material after process, influences the chemical property of synthetic material.And forerunner is prepared with carbonate co-precipitation
When body, metal ion all exists with stable carbonate form in presoma, but due to tri- metal ion species carbon of Ni, Mn, Co
The solubility product constant difference of hydrochlorate is larger, can inevitably lead to the small metal ion of solubility product and first precipitate, to cause into
Divide segregation.
Since the energy density of battery is limited by active material build-in attribute, while also by the shadow of extraneous factor
It rings, such as leads to lower lithium-ion-conducting since electrolyte wetability is bad, if the thickness of anode pole piece can be led when larger
Son is sent a telegraph from collector（Bottom）To positive plate（Top layer）Conduction is slower, these will affect the high rate performance of material, then study
Scholar is in order to improve the high rate performance of material, and by the way that single-layer carbon nano-tube and graphene etc. is added, but these can seriously increase life
Produce cost.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of lithium ion battery LiNixCoyMnl-x-yO2The system of positive electrode
Preparation Method, technological design is simple, not high to equipment requirement, it is easy to accomplish industrialized production.
The technical scheme is that：
A kind of lithium ion battery LiNixCoyMnl-x-yO2The preparation method of positive electrode, specifically includes following steps：
（1）, nickel source, cobalt source, manganese source, urea is dissolved in the mixed solvent in proportion, being then stirred makes in the mixed solvent
Component is uniformly dispersed to obtain mixed solution, then moves to mixed solution in autoclave, the successive reaction 8-24h at 120-180 DEG C,
It is cooled to centrifuge washing and drying after room temperature, Ni can be obtainedxCoyMnl-x-yCO3Presoma；Wherein, 0<X≤0.6,0<y≤
0.4；
（2）, by lithium source and NixCoyMnl-x-yCO3Presoma is added in dehydrated alcohol and is uniformly dispersed, dry, and grinding, heating is protected
Temperature, cooling, grinding, sieving obtains LiNixCoyMnl-x-yO2；
（3）, by LiNixCoyMnl-x-yO2, Kynoar, acetylene black, carbon fiber mixed in proportion, be rolled into 120 μ of thickness
The film of m obtains LiNi after 120 DEG C are dried in vacuo 10 hoursxCoyMnl-x-yO2Positive electrode.
The step（1）In, the nickel source selects nickel acetate, nickel sulfate, mixing one or more of in nickel nitrate；
The cobalt source is cobalt acetate, cobaltous sulfate, mixing one or more of in cobalt nitrate；The manganese source be manganese acetate, manganese sulfate,
One or more of mixing in manganese nitrate.
The step（1）In, the molar concentration of urea is 0.1-2mol/L.
The step（1）In, the in the mixed solvent include one of deionized water and dehydrated alcohol and
Ethylene glycol, wherein deionized water or the volume ratio of dehydrated alcohol and ethylene glycol are（0.5-2）:1.
The step（1）In, the centrifuge washing is washed respectively several times using deionized water and dehydrated alcohol.
The step（1）In, the revolving speed of centrifuge washing is 400-1000rpm, and drying temperature is 80-120 DEG C, when dry
Between be 8-12h.
The step（2）In, the lithium source selects lithium acetate, lithium sulfate, lithium nitrate, a kind of or several in lithium hydroxide
The mixing of kind.
The step（2）In, it is continuously heating to 300-600 DEG C after the grinding, keeps the temperature 4-8h, then be warming up to 700-
850 DEG C, 10-18h is kept the temperature, is cooled to room temperature, obtains LiNixCoyMnl-x-yO2Positive electrode.
The step（3）In, the quality of the carbon fiber accounts for LiNixCoyMnl-x-yO2The 3- of positive electrode gross mass
5%。
Advantages of the present invention：
（1）, the resulting LiNi of the present inventionxCoyMnl-x-yO2Positive electrode has more height ratio capacity, more preferable high rate performance；
（2）, the present invention standby Ni prepared using solvent/water thermal methodxCoyMnl-x-yCO3Presoma can make transition metal ions exist
It is uniformly dispersed in solvent, then is reacted by urea with water and generate ammonia and carbon dioxide, ammonia and water generate NH4 +And OH-, then
Carbon dioxide slowly generates carbonate under alkaline condition, and carbonate and transition metal ions react generation
NixCoyMnl-x-yCO3Presoma can avoid transition metal ions and segregation phenomena occurs, ensure that transition metal ions uniformly sinks
The Ni for forming sediment, while generatingxCoyMnl-x-yCO3Presoma has many advantages, such as that grain development is complete, granularity is small, and is evenly distributed.
（3）, the present invention in LiNixCoyMnl-x-yO2Addition carbon fiber, which can reduce, in the preparation process of positive electrode is produced into
This, while 3 dimension conductive networks of the carbon fiber composition being interweaved, the electric conductivity of material is improved, to improve the multiplying power of material
Performance.
Detailed description of the invention
Fig. 1 is LiNi prepared by the embodiment of the present invention 11/3Co1/3Mn1/3O2XRD diagram;
Fig. 2 is LiNi prepared by the embodiment of the present invention 21/3Co1/3Mn1/3O2FE-SEM figure;
Fig. 3 is LiNi prepared by the embodiment of the present invention 31/3Co1/3Mn1/3O2The first charge-discharge curve graph of positive electrode;
Fig. 4 is LiNi prepared by the embodiment of the present invention 31/3Co1/3Mn1/3O2The cycle performance figure of positive electrode;
Fig. 5 is the high rate performance figure of sample CF prepared by the embodiment of the present invention 4;
Fig. 6 is the high rate performance figure of sample Bare prepared by the embodiment of the present invention 4;
Fig. 7 is the electrochemical impedance spectroscopy (EIS) of sample CF and Bare prepared by the embodiment of the present invention 4.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
Embodiment 1
A kind of lithium ion battery LiNixCoyMnl-x-yO2The preparation method of positive electrode, specifically includes following steps：
（1）, 2.489g nickel acetate, 2.491g cobalt acetate, 2.451g manganese acetate, 2.4g urea are dissolved in the mixed of ethyl alcohol and ethylene glycol
In bonding solvent, the volume ratio of ethyl alcohol and ethylene glycol is 2:1, magnetic agitation 6h is then carried out, mixing speed 650rpm/min makes
The component of in the mixed solvent is uniformly dispersed, and then moves to mixed solution in the stainless steel autoclave containing polytetrafluoroethyllining lining,
The successive reaction 12h at 140 DEG C after being cooled to room temperature, is washed for several times, centrifugal rotational speed is respectively with deionized water and dehydrated alcohol
600rpm/min, 110 DEG C of dry 12h, grinding obtain Ni1/3Co1/3Mn1/3CO3Presoma；
（2）, by excessive LiOH and Ni1/3Co1/3Mn1/3CO3Presoma is added in dehydrated alcohol and is uniformly dispersed, drying and grinding
It is placed in Muffle furnace, the speed of 4 DEG C/min is warming up to 550 DEG C, keeps the temperature 4h, then be warming up to 850 DEG C, keeps the temperature 12h, is cooled to room
Temperature, grinding cross 450 meshes and obtain LiNi1/3Co1/3Mn1/3O2；
Fig. 1 is LiNi manufactured in the present embodiment1/3Co1/3Mn1/3O2X-ray diffraction spectrogram, from figure 1 it appears that
(006)/(102) and this two groups of peak divisions of (018)/(110) are obvious, other miscellaneous peaks do not occur, illustrate using solvent/water thermal method
The LiNi of preparation1/3Co1/3Mn1/3O2With good layer structure.
（3）, by LiNi1/3Co1/3Mn1/3O2, Kynoar（PVDF）, acetylene black press 84：8：8 mass ratio mixing is equal
It is even, it is rolled into thick 120 μm of film and obtains LiNi after 120 DEG C of vacuum drying 10h1/3Co1/3Mn1/3O2Positive electrode.
Using lmol/L LiPF6/ vinylacetate (EC)-diethyl acetate ester (DEC) be electrolyte, wherein EC with
The volume ratio 1 of DEC：1；Using metal lithium sheet as cathode；By LiNi in the dry glove box full of argon gas1/3Co1/3Mn1/ 3O2Positive electrode and electrolyte, cathode are assembled into battery.It is permanent to be carried out under 0.1C multiplying power to battery in 2.5-4.3V voltage range
Stream-constant-voltage charge, first discharge specific capacity is 156.4mAh/g when constant-current discharge under 0.2C multiplying power, but after 50 circulations
Capacity is only 123.7mAh/g.
Embodiment 2
（1）, 2.489g nickel acetate, 2.491g cobalt acetate, 2.451g manganese acetate, 2.4g urea is dissolved in deionized water and ethylene glycol
In the mixed solvent, the volume ratio of deionized water and ethylene glycol is 2:1, magnetic agitation 6h is then carried out, mixing speed is
650rpm/min makes the component of in the mixed solvent be uniformly dispersed, then moves to mixed solution containing polytetrafluoroethyllining lining not
It becomes rusty in steel autoclave, the successive reaction 12h at 140 DEG C after being cooled to room temperature, washs number with deionized water and dehydrated alcohol respectively
Secondary, centrifugal rotational speed 600rpm/min, 110 DEG C of dry 12h, grinding obtain Ni1/3Co1/3Mn1/3CO3Presoma；
（2）, by excessive LiOH and Ni1/3Co1/3Mn1/3CO3Presoma is added in dehydrated alcohol and is uniformly dispersed, drying and grinding
It is placed in Muffle furnace, the speed of 4 DEG C/min is warming up to 550 DEG C, keeps the temperature 4h, then be warming up to 850 DEG C, keeps the temperature 12h, is cooled to room
Temperature, grinding cross 450 meshes and obtain LiNi1/3Co1/3Mn1/3O2；
Fig. 2 is that the present embodiment prepares LiNi1/3Co1/3Mn1/3O2FE-SEM figure, as seen from Figure 2, the Ni of generationxCoyMnl-x- yCO3Presoma has many advantages, such as that grain development is complete, granularity is small, and is evenly distributed.
（3）, by LiNi1/3Co1/3Mn1/3O284 are pressed with PVDF, acetylene black, carbon fiber：8：5：3 mass ratio is uniformly mixed,
It is rolled into thick 120 μm of film, after 120 DEG C of vacuum drying 10h, obtains LiNi1/3Co1/3Mn1/3O2Positive electrode.
Using lmol/L LiPF6/ vinylacetate (EC)-diethyl acetate ester (DEC) be electrolyte, wherein EC with
The volume ratio 1 of DEC：1；Using metal lithium sheet as cathode；By LiNi in the dry glove box full of argon gas1/3Co1/3Mn1/ 3O2Positive electrode and electrolyte, cathode are assembled into battery.It is permanent to be carried out under 0.1C multiplying power to battery in 2.5-4.3V voltage range
Stream-constant-voltage charge, first discharge specific capacity is 160.2mAh/g when constant-current discharge under 0.2C multiplying power, is held after 50 circulations
Amount is 133.4mAh/g.
Embodiment 3
A kind of lithium ion battery LiNixCoyMnl-x-yO2The preparation method of positive electrode, specifically includes following steps：
（1）, 2.489g nickel acetate, 2.491g cobalt acetate, 2.451g manganese acetate, 2.4g urea is dissolved in deionized water and ethylene glycol
The volume ratio of in the mixed solvent, deionized water and ethylene glycol is 2:1, then carry out magnetic agitation 6h, mixing speed 650rpm/
Min makes the component of in the mixed solvent be uniformly dispersed, then mixed solution is moved to the stainless steel high pressure containing polytetrafluoroethyllining lining
In kettle, the successive reaction 10h at 160 DEG C after being cooled to room temperature, is washed for several times, centrifugation respectively with deionized water and dehydrated alcohol
Revolving speed is 600rpm/min, 110 DEG C of dry 12h, and grinding obtains Ni1/3Co1/3Mn1/3CO3Presoma；
（2）, by excessive LiOH and Ni1/3Co1/3Mn1/3CO3Presoma is added in dehydrated alcohol and is uniformly dispersed, drying and grinding
It is placed in Muffle furnace, the speed of 4 DEG C/min is warming up to 550 DEG C, keeps the temperature 4h, then be warming up to 850 DEG C, keeps the temperature 12h, is cooled to room
Temperature, grinding cross 450 meshes and obtain LiNi1/3Co1/3Mn1/3O2；
（3）, by LiNi1/3Co1/3Mn1/3O284 are pressed with PVDF, acetylene black, carbon fiber：8：5：3 mass ratio is uniformly mixed, and is rolled
At thick 120 μm of film, after 120 DEG C of vacuum drying 10h, LiNi is obtained1/3Co1/3Mn1/3O2Positive electrode.
Using lmol/L LiPF6/ vinylacetate (EC)-diethyl acetate ester (DEC) be electrolyte, wherein EC with
The volume ratio 1 of DEC：1；Using metal lithium sheet as cathode；By LiNi in the dry glove box full of argon gas1/3Co1/3Mn1/ 3O2Positive electrode and electrolyte, cathode are assembled into battery.Fig. 3 and Fig. 4 are seen, in 2.5-4.3V voltage range, under 0.1C multiplying power
Constant current-constant-voltage charge is carried out to battery, first discharge specific capacity is 164.7mAh/g when constant-current discharge under 0.2C multiplying power, through 50
Capacity is 141.4mAh/g, capacity retention ratio 85.9% after secondary circulation.
Embodiment 4
A kind of lithium ion battery LiNixCoyMnl-x-yO2The preparation method of positive electrode, specifically includes following steps：
（1）, 2.489g nickel acetate, 2.491g cobalt acetate, 2.451g manganese acetate, 2.4g urea is dissolved in deionized water and ethylene glycol
In the mixed solvent, the volume ratio of deionized water and ethylene glycol is 1:1, magnetic agitation 6h is then carried out, mixing speed is
650rpm/min makes the component of in the mixed solvent be uniformly dispersed, then moves to mixed solution containing polytetrafluoroethyllining lining not
It becomes rusty in steel autoclave, the successive reaction 10h at 160 DEG C after being cooled to room temperature, washs number with deionized water and dehydrated alcohol respectively
Secondary, centrifugal rotational speed 600rpm/min, 110 DEG C of dry 12h, grinding obtain Ni1/3Co1/3Mn1/3CO3Presoma；
（2）, by excessive LiOH and Ni1/3Co1/3Mn1/3CO3Presoma is added in dehydrated alcohol and is uniformly dispersed, drying and grinding
It is placed in Muffle furnace, the speed of 4 DEG C/min is warming up to 550 DEG C, keeps the temperature 4h, then be warming up to 850 DEG C, keeps the temperature 12h, is cooled to room
Temperature, grinding cross 450 meshes and obtain LiNi1/3Co1/3Mn1/3O2；
（3）,LiNi1/3Co1/3Mn1/3O2It is in mass ratio 84 with PVDF, acetylene black, carbon fiber：8：5：3 and 84：8：8：0 mixing
Uniformly, two different positive plates are made, claim sample CF and sample Bare respectively, wherein sample CF contains carbon fiber, sample
Bare does not contain carbon fiber；Sample CF and sample Bare be rolled into thick 120 μm of film, after 120 DEG C of vacuum drying 10h, obtains
To two kinds of LiNi1/3Co1/3Mn1/3O2Positive electrode.
Using lmol/L LiPF6/ vinylacetate (EC)-diethyl acetate ester (DEC) be electrolyte, wherein EC with
The volume ratio 1 of DEC：1；Using metal lithium sheet as cathode；By two kinds of LiNi in the dry glove box full of argon gas1/3Co1/ 3Mn1/3O2Positive electrode is assembled into battery with electrolyte, cathode respectively.
See Fig. 5 and Fig. 6, under comparison, the battery of sample CF assembling, in 2.5-4.3V voltage range, under 0.1C multiplying power into
Row constant current-constant-voltage charge, first discharge specific capacity is 162.2mAh/g when constant-current discharge under 0.2C multiplying power, is recycled by 50 times
Capacity is 138.4mAh/g afterwards.
See Fig. 7, the charge transfer resistance Rct of sample CF prepared by the present embodiment 4 is smaller, due to LiNi1/3Co1/3Mn1/ 3O2Carbon fiber in positive electrode improves electronic conductivity and inhibits the dissolution of transition metal ions, to improve LiNi1/ 3Co1/3Mn1/3O2The chemical property of positive electrode.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (9)
1. a kind of lithium ion battery LiNixCoyMnl-x-yO2The preparation method of positive electrode, it is characterised in that：It specifically includes following
Step：
（1）, using solvent/water thermal method prepare NixCoyMnl-x-yCO3Presoma：Nickel source, cobalt source, manganese source, urea is molten in proportion
In in the mixed solvent, being then stirred makes the component of in the mixed solvent be uniformly dispersed to obtain mixed solution, then by mixed solution
It moves in autoclave, the successive reaction 8-24h at 120-180 DEG C is cooled to centrifuge washing and drying after room temperature, can be obtained
NixCoyMnl-x-yCO3Presoma；Wherein, 0<X≤0.6,0<y≤0.4；
（2）, by lithium source and NixCoyMnl-x-yCO3Presoma is added in dehydrated alcohol and is uniformly dispersed, dry, and grinding, heating is protected
Temperature, cooling, grinding, sieving obtains LiNixCoyMnl-x-yO2；
（3）, by LiNixCoyMnl-x-yO2, Kynoar, acetylene black, carbon fiber mixed in proportion, be rolled into 120 μm thick
Film, 120 DEG C be dried in vacuo 10 hours after, obtain LiNixCoyMnl-x-yO2Positive electrode.
2. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（1）In, the nickel source selects nickel acetate, nickel sulfate, mixing one or more of in nickel nitrate；
The cobalt source is cobalt acetate, cobaltous sulfate, mixing one or more of in cobalt nitrate；The manganese source be manganese acetate, manganese sulfate,
One or more of mixing in manganese nitrate.
3. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（1）In, the molar concentration of urea is 0.1-2mol/L.
4. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（1）In, the in the mixed solvent include one of deionized water and dehydrated alcohol and
Ethylene glycol, wherein deionized water or the volume ratio of dehydrated alcohol and ethylene glycol are（0.5-2）:1.
5. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（1）In, the centrifuge washing is washed respectively several times using deionized water and dehydrated alcohol.
6. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（1）In, the revolving speed of centrifuge washing is 400-1000rpm, and drying temperature is 80-120 DEG C, when dry
Between be 8-12h.
7. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（2）In, the lithium source selects lithium acetate, lithium sulfate, lithium nitrate, a kind of or several in lithium hydroxide
The mixing of kind.
8. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（2）In, it is continuously heating to 300-600 DEG C after the grinding, keeps the temperature 4-8h, then be warming up to 700-
850 DEG C, 10-18h is kept the temperature, is cooled to room temperature, obtains LiNixCoyMnl-x-yO2Positive electrode.
9. a kind of lithium ion battery LiNi according to claim 1xCoyMnl-x-yO2The preparation method of positive electrode, it is special
Sign is：The step（3）In, the quality of the carbon fiber accounts for LiNixCoyMnl-x-yO2The 3- of positive electrode gross mass
5%。
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| CN110589904A (en) * | 2019-08-16 | 2019-12-20 | 南京理工大学 | Preparation method of spherical lithium-rich ternary cathode material |
| CN110957488A (en) * | 2019-11-07 | 2020-04-03 | 太原科技大学 | Preparation method of peanut-like nickel cobalt lithium manganate positive electrode material |
| CN112054182A (en) * | 2019-06-06 | 2020-12-08 | 惠州比亚迪实业有限公司 | Nickel cobalt lithium manganate ternary precursor and preparation method thereof, and nickel cobalt lithium manganate positive electrode material |
| CN113929155A (en) * | 2020-07-14 | 2022-01-14 | 中国科学院大连化学物理研究所 | Preparation method and application of lithium-rich manganese-based positive electrode material precursor |
| CN115832205A (en) * | 2021-11-02 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Positive electrode material pole piece, preparation method, secondary battery, battery module, battery pack and electric device |
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