CN109585843A - A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor - Google Patents
A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor Download PDFInfo
- Publication number
- CN109585843A CN109585843A CN201811336793.9A CN201811336793A CN109585843A CN 109585843 A CN109585843 A CN 109585843A CN 201811336793 A CN201811336793 A CN 201811336793A CN 109585843 A CN109585843 A CN 109585843A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- electrode material
- material precursor
- nickelic ternary
- nickel cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 50
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000004411 aluminium Substances 0.000 title claims abstract description 41
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000002243 precursor Substances 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 119
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 49
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000019441 ethanol Nutrition 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 159000000013 aluminium salts Chemical class 0.000 claims abstract description 14
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 4
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- -1 isothermal reaction Substances 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 229940077746 antacid containing aluminium compound Drugs 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 150000002500 ions Chemical class 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 238000000643 oven drying Methods 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229910017156 Ni0.80Co0.15Al0.05 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ACKHWUITNXEGEP-UHFFFAOYSA-N aluminum cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Co+2].[Ni+2] ACKHWUITNXEGEP-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007791 dehumidification Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 238000005303 weighing 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
-
- 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)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention discloses a kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor, and the nickel particle after cleaning is mixed with n,N-Dimethylformamide, ethylenediamine, according to last obtained nickelic tertiary cathode material Ni1‑y‑xCoyAlxStoichiometric ratio be added and cobalt salt and stir and evenly mix, isothermal reaction, product is taken out after cooling and is cleaned repeatedly with deionized water and ethyl alcohol, is dried in vacuo；Product is mixed with ethylene glycol, anhydrous ethylenediamine, aluminium salt is added according still further to stoichiometric ratio, isothermal reaction, cooled to room temperature, takes out product and clean, be dried in vacuo, obtain nickelic ternary nickel cobalt aluminium positive electrode material precursor powder Ni after reaction1‑y‑xCoyAlx；Nickel cobalt aluminium compounds precursors prepared by the present invention are regular spherical, and sphericity is preferable, epigranular, and tap density is high; it is suitable as the presoma of industrialized production anode material for lithium-ion batteries, simple process, degree of controllability is high, high yield rate; purity is high saves production cost, protects environment.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical fields, are specifically related to a kind of nickelic ternary nickel cobalt aluminium anode
The preparation method of material precursor.
Background technique
In order to meet the needs of people are to battery capacity, energy density, growing high rate performance, high-nickel material, which becomes, to be drawn
Lead one of the developing direction of the following anode material for lithium-ion batteries.LiNixCoyAl1-x-yO2Positive electrode combines LiNiO2With
LiCoO2The advantages of material.Co, A1 codope play the role of firm, the cationic mixing of inhibition, cyclical stability to material structure
Energy and security performance are greatly improved, and have the advantages that high capacity, high-energy density and good rate capability, can meet dynamic
Requirement of the power battery to positive electrode.The 18650 type batteries that tesla's Model-S electric vehicle uses, positive electrode are that group becomes
LiNi0.8Co0.15Al0.05O2, referred to as NCA, Japanese Toyota also applies this material on this general sharp plug-in hybrid electric vehicle.
The every physical and chemical performance and chemical property of positive electrode all with macroscopical physico-chemical property of its persursor material and micro-
The morphosis of sight is related.Therefore, it improves the order of persursor material crystal structure, optimize a grain form and secondary
Particle shape looks for improve tertiary cathode material every materialization and chemical property such as: tap density, cyclical stability, multiplying power are put
Electrical property etc. has vital influence.
Patent CN201310096403 is by the aqueous solution of sulfuric acid nickel salt, cobalt salt and aluminium salt, ammonia spirit (as complexing agent),
Sodium hydroxide solution (as precipitating reagent) and hydrazine hydrate solution (as antioxidant) are continuous through delicate flow control system respectively
Nickel cobalt aluminium presoma is obtained in injection reaction kettle, but due to Ni (OH)2(s) and Co (OH)2(s) KspIt is 10-14.7With 10-14.8, and Al (OH)3(s) KspIt is 10-33, Al (OH)3(s) settling velocity is far longer than Ni (OH)2(s) and Co (OH)2(s),
Tri- kinds of metallic elements of Ni, Co, Al are caused to cannot achieve uniform co-precipitation, and due to Al (OH)3(s) rapid precipitation can generate
A large amount of tiny nucleus, cause crystal that can not grow up, the presoma of micron particles required for cannot obtaining.Patent
CN201610014278 and CN201511023197 first prepares nickel cobalt co-precipitation hydroxide, then mixes aluminum contained compound sintering
Obtain nickel cobalt aluminum oxide.The method complex steps increase cost, and the nickel cobalt aluminum oxide tap density finally burnt is also inclined
It is low；And these methods use ammonium hydroxide as complexing agent, and ammonium hydroxide easily decomposes to give off ammonia, and temperature is higher, and decomposition rate is faster, can shape
At explosive atmosphere；The ammonia nitrogen compound that ammonium hydroxide is formed, pollutes the environment, causes centainly to injure to researcher.
Summary of the invention
In view of the presence of various technical problems, the present invention provides a kind of tap density height, good sphericity, Elemental redistribution are equal
The preparation method of even nickelic ternary nickel cobalt aluminium positive electrode material precursor, this method process is less, and cost is relatively low, and product quality is steady
Fixed, high degree of automation is suitble to industrialized production.
A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor, specifically includes the following steps:
(1) nickel particle after cleaning is put into polytetrafluoroethylene (PTFE) high pressure with N,N-dimethylformamide (DMF), ethylenediamine (EDA)
It is mixed in reaction kettle, according to last obtained nickelic ternary nickel cobalt aluminium positive electrode Ni1-y-xCoyAlxStoichiometric ratio add
Enter cobalt salt and stir and evenly mix, wherein 0 < y≤0.15, reaction kettle is put into baking oven and carries out isothermal reaction, instead by 0 x≤0.05 <
Cooled to room temperature after answering is taken out product and is cleaned repeatedly with deionized water and ethyl alcohol, then in a vacuum drying oven
It is dried in vacuo；
(2) product of step (1) is mixed with ethylene glycol, ethylenediamine (EDA), according still further to Ni1-y-xCoyAlxStoichiometric ratio
Aluminium salt is added, mixture is put into baking oven and carries out isothermal reaction, aluminium ion, reaction knot are introduced by the method for cation replacement
Cooled to room temperature after beam is taken out product and is cleaned repeatedly with deionized water and ethyl alcohol, then carried out in a vacuum drying oven
Vacuum drying obtains the high nickelic ternary nickel cobalt aluminium anode material of spherical shape of epigranular, high mechanical strength, good conductivity, porosity
Material precursor powder Ni1-y-xCoyAlx。
Step (1) nickel particle is the particle that the smashed partial size of nickel screen is 5 ~ 25 μm, and little particle is conducive to effects of ion
Displacement reaction, nickel particle cleaning is cleaned by ultrasonic using the mixed solution of alcohol and deionized water, and wash number is many
In 6 times, 10 ~ 15 minutes every time, the ratio of alcohol and deionized water was 1:1 in mixed solution.
Step (1) nickel particle and N,N-dimethylformamide (DMF), ethylenediamine (EDA) are according to nickel: N, N- dimethyl methyl
Amide (DMF): the molar ratio of ethylenediamine (EDA) is the mixing of 1:100 ~ 150:200 ~ 300.
Step (1) cobalt salt is the mixing of one or more of cobalt naphthenate, cobalt oxalate, cobalt acetate arbitrary proportion.
Step (1) and the temperature of step (2) isothermal reaction are 150 ~ 190 DEG C, and the time is 6 ~ 12h, the degree of ion exchange
It can be effectively controlled by adjusting time swap, the time is too short to make displacement reaction not exclusively, and ion can not be on matrix
Deposition.
Step (1) and step (2) vacuum drying temperature are 60 ~ 80 DEG C, the time is 12 ~ for 24 hours.
The product Yu ethylene glycol, ethylenediamine (EDA) of step (1) are according to the cobalt in the product of step (1) in step (2): second
Glycol: the molar ratio of ethylenediamine (EDA) is the mixing of 1:700 ~ 900:350 ~ 450.
Step (2) aluminium salt is aluminum sulfate, aluminum nitrate, sodium metaaluminate or aluminium chloride.
The invention has the following beneficial effects:
(1) for battery, the structure and pattern of coordination electrode material facilitate improving performance, and present invention selection has three
It ties up synthesizing activity material in the nickel screen substrate of skeleton and not only simplifies the preparation section of electrode, and help to increase the ratio of device
Capacity；It solves due to Ni (OH)2(s)、Co(OH)2(s) Ksp(respectively 10-14.7With 10-14.8) and Al (OH)3(s) Ksp
(10-33) tri- kinds of metallic elements of Ni, Co, Al the problem of cannot achieve uniform co-precipitation caused by gap is excessive, using a kind of simple
Solvent-thermal method synthesized micron ball in nickel screen substrate, the nucleation rate in crystallization process can be reduced, made in solution
The stoichiometrically co-precipitation of uniformly mixed each component effectively improves the order of material microstructure, improves sample
Bulk density.
(2) Ni, Co, Al in Ni, Co, Al elemental mole ratios and target molecule formula in nickel cobalt aluminium compound prepared by the present invention
Elemental mole ratios are identical, solve in nickel cobalt aluminium hydroxide precursor preparation in the prior art because of Al3+Cannot precipitate completely and
Caused by three kinds of nickel, cobalt, aluminium non-uniform problems of Elemental redistribution.
(3) nickel cobalt aluminium compounds precursors prepared by the present invention are regular spherical, and sphericity is preferable, epigranular, jolt ramming
Density height (2.35 ~ 2.88g/cm3), it is suitable as the presoma of industrialized production anode material for lithium-ion batteries.
(4) nickel cobalt aluminium compounds precursors prepared by the present invention are porous structure, increase the specific surface area of material, this is right
It is very useful in improving its chemical property.
(5) present invention process is simple, and degree of controllability is high, high yield rate, and purity is high saves production cost, protects environment.
Detailed description of the invention
Fig. 1 is product scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1；
Fig. 2 is the Discharge test curve for the first time that the embodiment of the present invention 1 is assembled into after battery；
Fig. 3 is the Discharge test curve for the first time that the embodiment of the present invention 2 is assembled into after battery；
Fig. 4 is the Discharge test curve for the first time that the embodiment of the present invention 3 is assembled into after battery.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments.
Embodiment 1
A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor, specifically includes the following steps:
It (1) is 5 ~ 10 μm by the partial size that nickel screen is crushed to nickel particle, little particle is conducive to the displacement reaction of effects of ion, nickel
Grain is cleaned by ultrasonic using the mixed solution of alcohol and deionized water, cleaning 6 times, and 15 minutes every time, alcohol in mixed solution
Ratio with deionized water is 1:1, by after cleaning nickel particle and n,N-Dimethylformamide (DMF), ethylenediamine (EDA) according to
Nickel: N,N-dimethylformamide (DMF): the molar ratio of ethylenediamine (EDA) is that 1:100:200 is mixed in polytetrafluoroethylene (PTFE) high pressure
In reaction kettle, according to last obtained nickelic ternary nickel cobalt aluminium positive electrode Ni1-y-xCoyAlxStoichiometric ratio be added cobalt
Salt simultaneously stirs and evenly mixs, wherein y=0.1, x=0.05, i.e., the molecular formula of nickelic ternary nickel cobalt aluminium positive electrode is
Ni0.85Co0.1Al0.05, cobalt salt is cobalt naphthenate, and reaction kettle is put into baking oven and carries out isothermal reaction, and the temperature of isothermal reaction is
150 DEG C, time 12h, the degree of ion exchange can be effectively controlled by adjusting time swap, and the time is too short to be made to set
Change reaction not exclusively, ion can not deposit on matrix, after reaction cooled to room temperature, take out product and use deionization
Water and ethyl alcohol clean repeatedly, are then dried in vacuo in a vacuum drying oven, and vacuum drying temperature is 60 DEG C, and the time is for 24 hours；
(2) by the product of step (1) and ethylene glycol, ethylenediamine (EDA) according to the cobalt in the product of step (1): ethylene glycol: second two
The molar ratio of amine (EDA) is 1:700:350 mixing, according still further to Ni0.85Co0.1Al0.05Stoichiometric ratio be added aluminium salt, aluminium salt
For aluminum sulfate, mixture is put into baking oven and carries out isothermal reaction, the temperature of isothermal reaction is 150 DEG C, and time 12h passes through
The method of cation replacement introduces aluminium ion, after reaction cooled to room temperature, takes out product and with deionized water and second
Alcohol cleans repeatedly, is then dried in vacuo in a vacuum drying oven, and vacuum drying temperature is 60 DEG C, and the time is for 24 hours, to obtain grain
Spend the high nickelic ternary nickel cobalt aluminium positive electrode material precursor powder of spherical shape of uniform, high mechanical strength, good conductivity, porosity
Ni0.85Co0.1Al0.05, tap density reach 2.54g/cm3。
Molar ratio is converted by detection: Ni, Co, Al member in Ni:Co:Al=0.85:0.1:0.05, with target molecule formula
Plain molar ratio is identical, illustrates that three kinds of nickel, cobalt, aluminium Elemental redistributions are uniform.
Fig. 1 show the scanning electron microscope (SEM) photograph for the product that the present embodiment is prepared, as can be seen from the figure the particle of sample
Pattern is uniform, and particle size is also relatively uniform, is 8 microns.
By the product of the present embodiment and a hydronium(ion) lithia according to a hydronium(ion) lithia and nickelic tertiary cathode material
Precursor powder Ni1-y-xCoyAlxMolar ratio be 1.05:1 ratio mixing after, in tube furnace, under oxygen atmosphere, with 2
DEG C/heating rate of min is warming up to 500 DEG C, 5h is kept the temperature, then the heating rate of 2 DEG C/min is warming up to 750 DEG C, keeps the temperature 15 hours,
Cool to room temperature with the furnace, obtain active substances in cathode materials after sintering, in the environment of desiccant dehumidification, by active material with
Nmp solvent, which is added, after being ground with the ratio weighing of 8:1:1 in PVDF, carbon black continues to grind, until forming sticky uniform slurry
Slurries are coated uniformly on above clean aluminium foil by liquid by slurries, and it is 80 DEG C pre- that duration 0.5h temperature is carried out in coating machine
Drying, puts it into continue to dry in vacuum oven later, keep 80 DEG C of dry 12h, appears finally by sheet-punching machine preparation
Product is 1.33cm2Positive plate, obtain the anode pole piece of button cell, full of high-purity argon gas glove box in carry out, with gold
Category lithium piece is cathode, and the UH20140 diaphragm of Teklon, LiPF6/EC+DMC+EMC(three's volume ratio of 1mol/L is 1:1:1)
Solution is electrolyte, is assembled into the button simulated battery of CR2025 model；Electric discharge for the first time at 0.1C (1C=200mAh/g) is surveyed
Test result curve, as shown in Figure 2.
Embodiment 2
A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor, specifically includes the following steps:
It (1) is 10 ~ 20 μm by the partial size that nickel screen is crushed to nickel particle, little particle is conducive to the displacement reaction of effects of ion, nickel
Particle is cleaned by ultrasonic using the mixed solution of alcohol and deionized water, cleaning 7 times, and 10 minutes every time, wine in mixed solution
The ratio of essence and deionized water is 1:1, and the nickel particle after cleaning is pressed with n,N-Dimethylformamide (DMF), ethylenediamine (EDA)
According to nickel: N,N-dimethylformamide (DMF): the molar ratio of ethylenediamine (EDA) is that 1:120:250 is mixed in polytetrafluoroethylene (PTFE) height
It presses in reaction kettle, according to last obtained nickelic ternary nickel cobalt aluminium positive electrode Ni1-y-xCoyAlxStoichiometric ratio be added
Cobalt salt simultaneously stirs and evenly mixs, wherein y=0.05, x=0.02, i.e., the molecular formula of nickelic ternary nickel cobalt aluminium positive electrode is
Ni0.93Co0.05Al0.02, cobalt salt is cobalt oxalate, and reaction kettle is put into baking oven and carries out isothermal reaction, and the temperature of isothermal reaction is
160 DEG C, time 10h, the degree of ion exchange can be effectively controlled by adjusting time swap, and the time is too short to be made to set
Change reaction not exclusively, ion can not deposit on matrix, after reaction cooled to room temperature, take out product and use deionization
Water and ethyl alcohol clean repeatedly, are then dried in vacuo in a vacuum drying oven, and vacuum drying temperature is 70 DEG C, time 15h；
(2) by the product of step (1) and ethylene glycol, ethylenediamine (EDA) according to the cobalt in the product of step (1): ethylene glycol: second two
The molar ratio of amine (EDA) is 1:900:450 mixing, according still further to Ni0.93Co0.05Al0.02Stoichiometric ratio be added aluminium salt, aluminium salt
For aluminum nitrate, mixture is put into baking oven and carries out isothermal reaction, the temperature of isothermal reaction is 160 DEG C, and time 12h passes through
The method of cation replacement introduces aluminium ion, after reaction cooled to room temperature, takes out product and with deionized water and second
Alcohol cleans repeatedly, is then dried in vacuo in a vacuum drying oven, and vacuum drying temperature is 70 DEG C, and time 16h obtains grain
Spend the high nickelic ternary nickel cobalt aluminium positive electrode material precursor powder of spherical shape of uniform, high mechanical strength, good conductivity, porosity
Ni0.93Co0.05Al0.02, tap density reach 2.35g/cm3。
Molar ratio is converted by detection: Ni, Co, Al member in Ni:Co:Al=0.93:0.05:0.02, with target molecule formula
Plain molar ratio is identical, illustrates that three kinds of nickel, cobalt, aluminium Elemental redistributions are uniform.
By the made presoma of the present embodiment, follow-up sintering and packed battery, button cell exist according to the method for embodiment 1
Discharge test curve for the first time under 0.1C (1C=200mAh/g), as shown in Figure 3.
Embodiment 3
A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor, specifically includes the following steps:
It (1) is 15 ~ 25 μm by the partial size that nickel screen is crushed to nickel particle, little particle is conducive to the displacement reaction of effects of ion, nickel
Particle is cleaned by ultrasonic using the mixed solution of alcohol and deionized water, cleaning 8 times, and 12 minutes every time, wine in mixed solution
The ratio of essence and deionized water is 1:1, and the nickel particle after cleaning is pressed with n,N-Dimethylformamide (DMF), ethylenediamine (EDA)
According to nickel: N,N-dimethylformamide (DMF): the molar ratio of ethylenediamine (EDA) is that 1:150:300 is mixed in polytetrafluoroethylene (PTFE) height
It presses in reaction kettle, according to last obtained nickelic ternary nickel cobalt aluminium positive electrode Ni1-y-xCoyAlxStoichiometric ratio be added
Cobalt salt simultaneously stirs and evenly mixs, wherein y=0.15, x=0.04, i.e., the molecular formula of nickelic ternary nickel cobalt aluminium positive electrode is
Ni0.81Co0.15Al0.04, cobalt salt is cobalt acetate, and reaction kettle is put into baking oven and carries out isothermal reaction, and the temperature of isothermal reaction is
190 DEG C, time 6h, the degree of ion exchange can be effectively controlled by adjusting time swap, and the time is too short to be made to set
Change reaction not exclusively, ion can not deposit on matrix, after reaction cooled to room temperature, take out product and use deionization
Water and ethyl alcohol clean repeatedly, are then dried in vacuo in a vacuum drying oven, and vacuum drying temperature is 80 DEG C, time 12h；
(2) by the product of step (1) and ethylene glycol, ethylenediamine (EDA) according to the cobalt in the product of step (1): ethylene glycol: second two
The molar ratio of amine (EDA) is 1:800:380 mixing, according still further to Ni0.81Co0.15Al0.04Stoichiometric ratio be added aluminium salt, aluminium salt
For aluminium chloride, mixture is put into baking oven and carries out isothermal reaction, the temperature of isothermal reaction is 190 DEG C, and time 6h passes through sun
The method of ion exchange introduces aluminium ion, after reaction cooled to room temperature, takes out product and with deionized water and ethyl alcohol
It cleans, is then dried in vacuo in a vacuum drying oven repeatedly, vacuum drying temperature is 80 DEG C, and time 12h obtains granularity
Uniformly, the high nickelic ternary nickel cobalt aluminium positive electrode material precursor powder of spherical shape of high mechanical strength, good conductivity, porosity
Ni0.81Co0.15Al0.04, tap density reach 2.88g/cm3。
Molar ratio is converted by detection: Ni, Co, Al member in Ni:Co:Al=0.81:0.15:0.04, with target molecule formula
Plain molar ratio is identical, illustrates that three kinds of nickel, cobalt, aluminium Elemental redistributions are uniform.
By the made presoma of the present embodiment, follow-up sintering and packed battery, button cell exist according to the method for embodiment 1
Discharge test curve for the first time under 0.1C (1C=200mAh/g), as shown in Figure 4.
Embodiment 4
A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor, specifically includes the following steps:
It (1) is 10 ~ 15 μm or so by the partial size that nickel screen is crushed to nickel particle, nickel particle is molten using the mixing of alcohol and deionized water
Liquid is cleaned by ultrasonic, and is cleaned 7 times, 11 minutes every time, the ratio of alcohol and deionized water was 1:1 in mixed solution, will be cleaned
Nickel particle afterwards is with N,N-dimethylformamide (DMF), ethylenediamine (EDA) according to nickel (Ni): N,N-dimethylformamide
(DMF): the molar ratio of ethylenediamine (EDA) is that 1:120:250 is mixed in polytetrafluoroethylene (PTFE) autoclave, according to last institute
Obtained nickelic ternary nickel cobalt aluminium positive electrode Ni1-y-xCoyAlxStoichiometric ratio be added and cobalt salt and stir and evenly mix, wherein y=
0.15, x=0.05, i.e., the molecular formula of nickelic ternary nickel cobalt aluminium positive electrode is Ni0.80Co0.15Al0.05, cobalt salt is cobalt oxalate and vinegar
Reaction kettle is put into baking oven according to the salt-mixture of molar ratio 1:1 and carries out isothermal reaction by sour cobalt, and the temperature of isothermal reaction is 180
DEG C, time 7h, the degree of ion exchange can be effectively controlled by adjusting time swap, and the time is too short to make displacement anti-
Should not exclusively, ion can not deposit on matrix, after reaction cooled to room temperature, take out product and with deionized water with
Ethyl alcohol cleans repeatedly, is then dried in vacuo in a vacuum drying oven, and vacuum drying temperature is 70 DEG C, time 15h；
(2) by the product of step (1) and ethylene glycol, ethylenediamine (EDA) according to the cobalt in the product of step (1): ethylene glycol: second two
The molar ratio of amine (EDA) is 1:780:400 mixing, according still further to Ni0.80Co0.15Al0.05Stoichiometric ratio be added aluminium salt, aluminium salt
For aluminum nitrate, mixture is put into baking oven and carries out isothermal reaction, the temperature of isothermal reaction is 150 DEG C, and time 12h passes through
The method of cation replacement introduces aluminium ion, after reaction cooled to room temperature, takes out product and with deionized water and second
Alcohol cleans repeatedly, is then dried in vacuo in a vacuum drying oven, and vacuum drying temperature is 80 DEG C, and time 12h obtains grain
Spend the high nickelic ternary nickel cobalt aluminium positive electrode material precursor powder of spherical shape of uniform, high mechanical strength, good conductivity, porosity
Ni0.80Co0.15Al0.05, tap density reach 2.66g/cm3。
Molar ratio is converted by detection: Ni, Co, Al member in Ni:Co:Al=0.80:0.15:0.05, with target molecule formula
Plain molar ratio is identical, illustrates that three kinds of nickel, cobalt, aluminium Elemental redistributions are uniform.
Claims (8)
1. a kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor, which is characterized in that specifically includes the following steps:
(1) nickel particle after cleaning is mixed with n,N-Dimethylformamide, ethylenediamine, according to last obtained nickelic ternary
Nickel cobalt aluminium positive electrode Ni1-y-xCoyAlxStoichiometric ratio be added and cobalt salt and stir and evenly mix, wherein 0 < y≤0.15,0 < x≤
0.05, isothermal reaction, cooled to room temperature, takes out product and is cleaned repeatedly with deionized water and ethyl alcohol, so after reaction
After be dried in vacuo；
(2) product of step (1) is mixed with ethylene glycol, ethylenediamine, according still further to Ni1-y-xCoyAlxStoichiometric ratio be added aluminium
Salt, isothermal reaction, cooled to room temperature, takes out product and is cleaned repeatedly with deionized water and ethyl alcohol, then after reaction
Vacuum drying, obtains nickelic ternary nickel cobalt aluminium positive electrode material precursor powder Ni1-y-xCoyAlx。
2. the preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor according to claim 1, which is characterized in that step
(1) it is 5 ~ 25 μm of particle that nickel particle, which is the smashed partial size of nickel screen, and nickel particle cleaning is using the mixed of alcohol and deionized water
Solution to be closed to be cleaned by ultrasonic, wash number is no less than 6 times, and 10 ~ 15 minutes every time, alcohol and deionized water in mixed solution
Ratio is 1:1.
3. the preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor according to claim 1, which is characterized in that step
(1) nickel particle and N,N-dimethylformamide, ethylenediamine are according to nickel: N,N-dimethylformamide: the molar ratio of ethylenediamine is 1:
The ratio of 100 ~ 150:200 ~ 300 mixes.
4. the preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor according to claim 1, which is characterized in that step
(1) cobalt salt is the mixing of one or more of cobalt naphthenate, cobalt oxalate, cobalt acetate arbitrary proportion.
5. the preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor according to claim 1, which is characterized in that step
(1) and the temperature of step (2) isothermal reaction is 150 ~ 190 DEG C, and the time is 6 ~ 12h.
6. the preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor according to claim 1, which is characterized in that step
(1) and step (2) vacuum drying temperature be 60 ~ 80 DEG C, the time be 12 ~ for 24 hours.
7. the preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor according to claim 1, which is characterized in that step
(2) product Yu ethylene glycol, ethylenediamine of step (1) are according to the cobalt in the product of step (1) in: ethylene glycol: mole of ethylenediamine
Than the ratio mixing for 1:700 ~ 900:350 ~ 450.
8. the preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor according to claim 1, which is characterized in that step
(2) aluminium salt is aluminum sulfate, aluminum nitrate, sodium metaaluminate or aluminium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811336793.9A CN109585843B (en) | 2018-11-12 | 2018-11-12 | Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811336793.9A CN109585843B (en) | 2018-11-12 | 2018-11-12 | Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109585843A true CN109585843A (en) | 2019-04-05 |
| CN109585843B CN109585843B (en) | 2021-09-21 |
Family
ID=65922027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811336793.9A Active CN109585843B (en) | 2018-11-12 | 2018-11-12 | Preparation method of high-nickel ternary nickel-cobalt-aluminum positive electrode material precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109585843B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111834631A (en) * | 2020-07-13 | 2020-10-27 | 万华化学集团股份有限公司 | Preparation method of high-nickel cathode material of lithium ion battery |
| CN112510194A (en) * | 2019-09-16 | 2021-03-16 | 惠州比亚迪实业有限公司 | Ternary cathode material of lithium ion battery, preparation method of ternary cathode material and lithium ion battery |
| CN114906885A (en) * | 2022-05-23 | 2022-08-16 | 青海师范大学 | High-rate positive electrode material of lithium ion battery and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
| CN101428349A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Method for producing nickel-cobalt metal powder |
| CN102569782A (en) * | 2010-12-30 | 2012-07-11 | 河南科隆集团有限公司 | Cobalt-aluminum-doped nickel oxyhydroxide and preparation method thereof |
| CN102931396A (en) * | 2012-11-05 | 2013-02-13 | 湖南丰日电源电气股份有限公司 | Anode material for high-performance alkaline batteries and method for preparing anode material |
| CN103178262A (en) * | 2011-12-23 | 2013-06-26 | 西安物华新能源科技有限公司 | Method for preparing aluminum-nickel-lithium cobalt oxide-doped anode material |
| CN104658766A (en) * | 2015-02-12 | 2015-05-27 | 南京工业大学 | Silicon nanosheet doped nickel cobaltate and preparation method thereof |
| CN105552361A (en) * | 2016-01-25 | 2016-05-04 | 荆门市格林美新材料有限公司 | Positive electrode material precursor of lithium ion battery and preparation method thereof |
| CN107195471A (en) * | 2017-06-01 | 2017-09-22 | 上海应用技术大学 | A kind of preparation method of the Ni-based combination electrode materials of porous C oAl@ |
| JP2018181829A (en) * | 2017-04-18 | 2018-11-15 | 太平洋セメント株式会社 | Manufacturing method of negative electrode active material for lithium ion secondary battery |
-
2018
- 2018-11-12 CN CN201811336793.9A patent/CN109585843B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
| CN101428349A (en) * | 2008-07-29 | 2009-05-13 | 张建玲 | Method for producing nickel-cobalt metal powder |
| CN102569782A (en) * | 2010-12-30 | 2012-07-11 | 河南科隆集团有限公司 | Cobalt-aluminum-doped nickel oxyhydroxide and preparation method thereof |
| CN103178262A (en) * | 2011-12-23 | 2013-06-26 | 西安物华新能源科技有限公司 | Method for preparing aluminum-nickel-lithium cobalt oxide-doped anode material |
| CN102931396A (en) * | 2012-11-05 | 2013-02-13 | 湖南丰日电源电气股份有限公司 | Anode material for high-performance alkaline batteries and method for preparing anode material |
| CN104658766A (en) * | 2015-02-12 | 2015-05-27 | 南京工业大学 | Silicon nanosheet doped nickel cobaltate and preparation method thereof |
| CN105552361A (en) * | 2016-01-25 | 2016-05-04 | 荆门市格林美新材料有限公司 | Positive electrode material precursor of lithium ion battery and preparation method thereof |
| JP2018181829A (en) * | 2017-04-18 | 2018-11-15 | 太平洋セメント株式会社 | Manufacturing method of negative electrode active material for lithium ion secondary battery |
| CN107195471A (en) * | 2017-06-01 | 2017-09-22 | 上海应用技术大学 | A kind of preparation method of the Ni-based combination electrode materials of porous C oAl@ |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112510194A (en) * | 2019-09-16 | 2021-03-16 | 惠州比亚迪实业有限公司 | Ternary cathode material of lithium ion battery, preparation method of ternary cathode material and lithium ion battery |
| CN111834631A (en) * | 2020-07-13 | 2020-10-27 | 万华化学集团股份有限公司 | Preparation method of high-nickel cathode material of lithium ion battery |
| CN114906885A (en) * | 2022-05-23 | 2022-08-16 | 青海师范大学 | High-rate positive electrode material of lithium ion battery and preparation method thereof |
| CN114906885B (en) * | 2022-05-23 | 2024-02-02 | 青海师范大学 | High-magnification positive electrode material of lithium ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109585843B (en) | 2021-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102386391B (en) | Method for preparing ternary complex anode material (LiNixCoyMn1-x-yO2) | |
| CN103482711B (en) | A kind of ultrasonic wave added prepares the method for ternary cathode material of lithium ion battery presoma | |
| CN105304893A (en) | Preparation method of lithium ion battery anode active material lithium nickel manganese oxide | |
| CN109301240A (en) | Nickelic multicomponent material presoma of cation doping gradient and its preparation method and application | |
| CN106654210B (en) | A kind of nickelic positive electrode of high temperature long circulating lithium ion battery and preparation method thereof | |
| CN109461927A (en) | A kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof | |
| CN104752714A (en) | High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method thereof | |
| CN105514373A (en) | Positive electrode material of high-capacity lithium ion battery and preparation method of positive electrode material | |
| CN104466158A (en) | Lithium-rich positive electrode material and preparation method thereof | |
| CN109994728A (en) | The one nickelic positive electrode and preparation method thereof with uniform clad | |
| CN112234169B (en) | Lithium ion battery positive electrode material, preparation method thereof and lithium ion battery | |
| CN111129485A (en) | Single-crystal high-nickel ternary cathode material and preparation method thereof | |
| CN111087031B (en) | Preparation method of coated positive electrode material | |
| CN109585843A (en) | A kind of preparation method of nickelic ternary nickel cobalt aluminium positive electrode material precursor | |
| CN104600285A (en) | Method for preparing spherical lithium nickel manganese oxide positive pole material | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| CN110085831A (en) | A kind of metatitanic acid lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof | |
| CN103560227A (en) | Preparation method of Li4Ti5O12/C composite material | |
| CN109950523A (en) | Lithium ion battery negative material transition metal oxide/carbon preparation method | |
| CN107887583A (en) | A kind of doped lithium iron phosphate anode material and preparation method thereof | |
| CN112744872A (en) | Liquid-phase phosphorus element doping modification preparation method of high-nickel anode material | |
| CN108565458A (en) | A kind of preparation method and applications of nickel cobalt aluminium tertiary cathode material | |
| CN108511724A (en) | A kind of collosol and gel auxiliary supercritical CO2Drying prepares iron manganese phosphate for lithium method | |
| CN105336944A (en) | High-capacity cathode material for lithium ion batteries and preparation method thereof | |
| EP4113660A1 (en) | Method for preparing material having composition gradient characteristic, and application in battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |