CN107968201A - A kind of preparation method of anode material for lithium-ion batteries and its presoma - Google Patents
A kind of preparation method of anode material for lithium-ion batteries and its presoma Download PDFInfo
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- CN107968201A CN107968201A CN201611256094.4A CN201611256094A CN107968201A CN 107968201 A CN107968201 A CN 107968201A CN 201611256094 A CN201611256094 A CN 201611256094A CN 107968201 A CN107968201 A CN 107968201A
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- Prior art keywords
- lithium
- ion batteries
- anode material
- preparation
- presoma
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 239000010405 anode material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000004411 aluminium Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000012670 alkaline solution Substances 0.000 claims abstract description 22
- 238000009938 salting Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 159000000013 aluminium salts Chemical class 0.000 claims description 5
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [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 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000012065 filter cake Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000000975 co-precipitation Methods 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910012391 LiCo0.99Al0.01O2 Inorganic materials 0.000 description 1
- 229910016191 LiNi0.9Al0.1O2 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 washing Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides the preparation method of a kind of anode material for lithium-ion batteries and its presoma.By salting liquid, cocurrent is added in the reaction kettle of carry potential overflow mouth and is reacted the alkaline solution containing aluminium element, ammonium hydroxide together, the precursor pulp that overflow obtains is by separation of solid and liquid, washing, drying, screening, uniformly mixed the presoma of aluminium, then the presoma is mixed with lithium source, sintered, crushed, sieved, uniformly mixed the positive electrode of aluminium.This method can realize the Uniform Doped of aluminium element, and technique is simple, and the easy stability contorting of process, production cost is low, suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the preparation method of a kind of anode material for lithium-ion batteries and its presoma, in particular to one kind
Mix the anode material for lithium-ion batteries of aluminium and its preparation method of presoma.
Background technology
Lithium ion battery is green high-capacity battery, has that voltage is high, energy density is big, good cycle, self discharge are small, nothing
Outstanding advantages of memory effect, be widely used in various portable power tools, electronic instrument, mobile phone, laptop,
Video camera, weaponry etc., in electric automobile and all kinds of energy storage fields also large-scale use.
In recent years, the yield of lithium ion battery is skyrocketed through, and application field constantly expands, and market is to lithium ion battery energy
The requirement of density is higher and higher, needs that the energy density of anode material for lithium-ion batteries is continuously improved accordingly, but with material
The raising of energy density, its cycle performance, security performance decline therewith, how in the case where not sacrificing capacity, improve at the same time
It is circulated and security performance, becomes urgent problem to be solved.
The main method of modifying for improving anode material for lithium-ion batteries circulation and security performance at present is doping and cladding, its
Middle doping aluminium element can be with stabilizing material structure, hence it is evident that suppresses the exothermic reaction in charge and discharge process, can effectively improve just
Pole material circulation and security performance.Chemical coprecipitation synthesis mix the positive electrode material precursor of aluminium when, due to nickel cobalt manganese element with
The precipitation pH of aluminium element differs greatly, the maximum difference 10 of solubility product constant18Times, while trivalent aluminium is difficult to be complexed with ammonium hydroxide,
So using conventional liquid-phase coprecipitation, aluminium easily generates fluffy solid, causes to mix aluminium element skewness in aluminium presoma
It is even, while conventional liquid-phase coprecipitation usually distinguishes the salting liquids such as nickel cobalt manganese, aluminum salt solution, aqueous slkali, enveloping agent solution
Add reaction kettle to be reacted, not only process control difficulties are big, and product index stability is poor, and equipment investment is more, of high cost.
The content of the invention
The preparation method of a kind of anode material for lithium-ion batteries and its presoma provided by the invention, this method can be realized
The Uniform Doped of aluminium element, properties of product are obviously improved, and technique is simple, and process control is easy, can compare appearance
Control reaction system of changing places and the stability of product index, production cost is low, is more suitable for large-scale industrial production.
Technical scheme is as follows：
A kind of preparation method of anode material for lithium-ion batteries and its presoma, includes the following steps：
（1）One or more of metal salts containing Ni, Co, Mn element are configured to the salting liquid that concentration is 1-3mol/L, will
Aluminium salt, alkali, ammonium hydroxide are mixed in a certain ratio the alkaline solution for being configured to that concentration is 2-10mol/L；
（2）By step（1）In salting liquid, alkaline solution solution together cocurrent be added in the reaction kettle of carry potential overflow mouth carry out it is anti-
Should, process is kept stirring, while control salting liquid and alkaline solution is 40-70 DEG C into flow quantity, reaction temperature, and overflow obtains
Precursor pulp after separation of solid and liquid, washing, drying, screening, uniformly mixed the spherical precursor of aluminium；
（3）By step（2）In obtained presoma mixed with lithium source, in air or oxygen atmosphere, sintered at 700-1150 DEG C
4-20h, by broken, screening, obtains anode material for lithium-ion batteries.
In above-mentioned preparation method, the anode material for lithium-ion batteries general formula is：
LiNixCoyMnzAldO2
Wherein, 0≤x<1,0≤y<1,0≤z<1,0.001≤d≤0.1, x+y+z+d=1.
In above-mentioned preparation method, the precursor formula is：
NixCoyMnzAld(OH)2+d
Wherein, 0≤x<1,0≤y<1,0≤z<1,0.001≤d≤0.1, x+y+z+d=1.
In above-mentioned preparation method, step（1）Described in metal salt be sulfate, chlorate, nitrate, in acetate
It is a kind of or wherein several.
In above-mentioned preparation method, step（1）Described in aluminium salt be aluminum sulfate, aluminum nitrate, one kind in aluminium chloride or wherein
It is several.
In above-mentioned preparation method, step（1）Described in alkali be sodium hydroxide, one or both of potassium hydroxide.
In above-mentioned preparation method, step（2）Reaction process can be to being passed through nitrogen in reaction kettle.
In above-mentioned preparation method, step（3）Described in lithium source be lithium carbonate, lithium hydroxide and lithium nitrate in one kind or
It is wherein several.
Present invention tool has the advantage that：
Compared with prior art, aluminium salt and sodium hydroxide, ammonium hydroxide are first hybridly prepared into certain density containing aluminium alkalescence by the present invention
Solution.Aluminium element settling velocity slows down in one side reaction process, so as to realize uniformly co-precipitation with nickel cobalt manganese element；The opposing party
Face reaction process only needs control salting liquid with alkaline solution both solution into flow quantity, and technique is simple, can be easier
Control reaction system and product index stability, so as to fulfill the continuous and stable production of product.
Brief description of the drawings
Fig. 1 is a kind of made scanning electron microscope of precursor of lithium ionic cell positive material of the embodiment of the present invention 1
（SEM）Figure.
Fig. 2 sweeps for a kind of made element line of precursor of lithium ionic cell positive material particle section of the embodiment of the present invention 1
Retouch electron microscope（SEM）Figure.
Fig. 3 is the energy spectrum analysis of aluminium element in a kind of made precursor of lithium ionic cell positive material of the embodiment of the present invention 1
（EDS）Figure.
Fig. 4 is a kind of made scanning electron microscope of anode material for lithium-ion batteries of the embodiment of the present invention 1（SEM）Figure.
Embodiment
It will be helpful to understand the present invention by following embodiments and attached drawing, but do not limit present disclosure.
Embodiment 1
By nickel sulfate, cobaltous sulfate according to metal molar than 87：10 ratio dissolves to obtain the mixing salt solution of 2mol/L；By nitric acid
Aluminium, sodium hydroxide, ammonium hydroxide are according to molar ratio 3：204：50 ratio dissolves to obtain the alkaline solution of 4mol/L.Salting liquid, alkalescence
Solution is respectively put into different vessels, and two kinds of solution together cocurrent are added in the reaction kettle of carry potential overflow mouth, and process is kept
Stirring, the salting liquid flow for controlling reaction system are 0.97L/h, and alkaline solution flow is 1.29L/h, and reaction temperature is 50 DEG C,
The precursor pulp that continuous overflow obtains is sieved after drying 10h, obtained by filter press separation of solid and liquid, washing, 105 DEG C of filter cake
The even spherical precursor for mixing aluminium.By above-mentioned persursor material and lithium hydroxide mixed ingredients, in oxygen atmosphere, 760 DEG C of sintering
12h, by broken, screening, obtains anode material for lithium-ion batteries LiNi0.87Co0.1Al0.03O2。
Embodiment 2
By nickel nitrate, cobaltous sulfate, manganese chloride according to metal molar than 80：10：The salt-mixture that 9 ratio dissolves to obtain 1mol/L is molten
Liquid；By aluminium chloride, sodium hydroxide, ammonium hydroxide according to molar ratio 1：203：35 ratio dissolves to obtain the alkaline solution of 6mol/L.Salt
Solution, alkaline solution are respectively put into different vessels, and two kinds of solution together cocurrent are added in the reaction kettle of carry potential overflow mouth,
In N2Reacted under atmosphere protection, process is kept stirring, and the salting liquid flow for controlling reaction system is 1.98L/h, and alkalescence is molten
Flow quantity is 0.8L/h, and reaction temperature is 55 DEG C, and the precursor pulp that continuous overflow obtains is passed through filter press separation of solid and liquid, washed
Wash, sieved after 115 DEG C of drying 5h of filter cake, uniformly mixed the spherical precursor of aluminium.By above-mentioned persursor material and lithium hydroxide
Mixed ingredients, in oxygen atmosphere, 760 DEG C of sintering 10h, by broken, screening, obtain anode material for lithium-ion batteries
LiNi0.8Co0.1 Mn0.09Al0.01O2。
Embodiment 3
Nickel sulfate is dissolved to obtain the salting liquid of 2.5mol/L；By aluminum sulfate, sodium hydroxide, ammonium hydroxide according to molar ratio 5：105：30
Ratio dissolve to obtain the alkaline solution of 8mol/L.Salting liquid, alkaline solution are respectively put into different vessels, and by two kinds of solution
Cocurrent is added in the reaction kettle of carry potential overflow mouth together, and process is kept stirring, and the salting liquid flow for controlling reaction system is 1.8L/
H, alkaline solution flow are 1.75L/h, and reaction temperature is 50 DEG C, and the precursor pulp that continuous overflow obtains passes through filter press solid-liquid
Separation, washing, 115 DEG C of filter cake sieve after drying 5h, are uniformly mixed the spherical precursor of aluminium.By above-mentioned persursor material and hydrogen
Lithia mixed ingredients, in oxygen atmosphere, 740 DEG C of sintering 15h, by broken, screening, obtain anode material for lithium-ion batteries
LiNi0.9Al0.1O2。
Embodiment 4
By nickel chloride, manganese sulfate according to metal molar than 49：49 ratio dissolves to obtain the mixing salt solution of 3mol/L；By nitric acid
Aluminium, sodium hydroxide, ammonium hydroxide are according to molar ratio 1：101：12 ratio dissolves to obtain the alkaline solution of 10mol/L.Salting liquid, alkalescence
Solution is respectively put into different vessels, and two kinds of solution together cocurrent are added in the reaction kettle of carry potential overflow mouth, in N2Atmosphere
Reacted under protection, process is kept stirring, and the salting liquid flow for controlling reaction system is 0.98L/h, and alkaline solution flow is
0.68L/h, reaction temperature are 45 DEG C, and the precursor pulp that continuous overflow obtains is by centrifuge separation of solid and liquid, washing, filter cake
Sieved after 120 DEG C of drying 5h, uniformly mixed the spherical precursor of aluminium.By above-mentioned persursor material and lithium carbonate mixed ingredients,
In air atmosphere, 890 DEG C of sintering 14h, by broken, screening, obtain anode material for lithium-ion batteries
LiNi0.49Mn0.49Al0.02O2。
Embodiment 5
By nickel acetate, cobalt acetate, manganese acetate according to metal molar than 60：19.8：19.8 ratio dissolves to obtain 1.5mol/L's
Mixing salt solution；By aluminum sulfate, sodium hydroxide, ammonium hydroxide according to molar ratio 1：1010：230 ratio dissolves to obtain the alkali of 3mol/L
Property solution.Salting liquid, alkaline solution are respectively put into different vessels, and two kinds of solution together cocurrent are added to carry potential overflow mouth
In reaction kettle, in N2Reacted under atmosphere protection, process is kept stirring, and the salting liquid flow for controlling reaction system is
1.992L/h, alkaline solution flow are 2.48L/h, and reaction temperature is 60 DEG C, and the precursor pulp that continuous overflow obtains is through overvoltage
Filter separation of solid and liquid, washing, 110 DEG C of filter cake sieve after drying 5h, are uniformly mixed the spherical precursor of aluminium.By above-mentioned presoma
Material and lithium carbonate mixed ingredients, in air atmosphere, 850 DEG C of sintering 5h, by broken, screening, are obtaining lithium ion battery just
Pole material LiNi0.6Co0.198Mn0.198Al0.004O2。
Embodiment 6
Cobalt chloride is dissolved to obtain the salting liquid of 3mol/L；By aluminum nitrate, sodium hydroxide, ammonium hydroxide according to molar ratio 1：618：90
Ratio dissolves to obtain the alkaline solution of 2mol/L.Salting liquid, alkaline solution are respectively put into different vessels, and by two kinds of solution one
Play cocurrent to be added in the reaction kettle of carry potential overflow mouth, in N2Reacted under atmosphere protection, process is kept stirring, and controls reactant
The salting liquid flow of system is 2.18L/h, and alkaline solution flow is 7.82L/h, and reaction temperature is 65 DEG C, before continuous overflow obtains
Drive somaplasm material to sieve after drying 6h by centrifuge separation of solid and liquid, washing, 130 DEG C of filter cake, uniformly mixed the spherical forerunner of aluminium
Body.By above-mentioned persursor material and lithium carbonate mixed ingredients, in air atmosphere, 1120 DEG C sinter 14h, by crushing, sieving,
Obtain anode material for lithium-ion batteries LiCo0.99Al0.01O2。
Embodiment 7
By nickel chloride, cobaltous sulfate, manganese nitrate according to metal molar than 50：20：29.7 ratio dissolves to obtain the mixing of 2mol/L
Salting liquid；By aluminum nitrate, sodium hydroxide, ammonium hydroxide according to molar ratio 1：700：55 ratio dissolves to obtain the alkaline molten of 8mol/L
Liquid.Salting liquid, alkaline solution are respectively put into different vessels, and two kinds of solution together cocurrent are added to the reaction of carry potential overflow mouth
In kettle, in N2Reacted under atmosphere protection, process is kept stirring, and the salting liquid flow for controlling reaction system is 2.28L/h, alkali
Property liquid inventory be 1.295L/h, reaction temperature is 55 DEG C, and the precursor pulp that continuous overflow obtains is by filter press solid-liquid point
From, washing, sieved after 120 DEG C of filter cake drying 8h, uniformly mixed the spherical precursor of aluminium.Even by above-mentioned persursor material and carbon
Sour lithium mixed ingredients, in air atmosphere, 900 DEG C of sintering 20h, by broken, screening, obtain anode material for lithium-ion batteries
LiNi0.50Co0.20Mn0.297Al0.003O2。
Claims (8)
1. the preparation method of a kind of anode material for lithium-ion batteries and its presoma, comprises the following steps：（1）Will contain Ni,
One or more of metal salts of Co, Mn element are configured to the salting liquid that concentration is 1-3mol/L, and aluminium salt, alkali, ammonium hydroxide are pressed one
Certainty ratio is hybridly prepared into the alkaline solution that concentration is 2-10mol/L；（2）By step（1）In salting liquid, alkaline solution solution
Cocurrent is added in the reaction kettle of carry potential overflow mouth and is reacted together, and process is kept stirring, while controls salting liquid molten with alkalescence
Liquid into flow quantity, reaction temperature is 40-70 DEG C, and the precursor pulp that overflow obtains is by separation of solid and liquid, washing, drying, sieve
After point, the spherical precursor of aluminium is uniformly mixed；（3）By step（2）In obtained presoma mixed with lithium source, in air or oxygen
In gas atmosphere, 4-20h is sintered at 700-1150 DEG C, by broken, screening, obtains anode material for lithium-ion batteries.
2. the preparation method of anode material for lithium-ion batteries and its presoma according to claim 1, it is characterised in that described
Anode material for lithium-ion batteries general formula be：LiNixCoyMnzAldO2Wherein, 0≤x<1,0≤y<1,0≤z<1,0.001≤d
≤ 0.1, x+y+z+d=1.
3. the preparation method of anode material for lithium-ion batteries and its presoma according to claim 1, it is characterised in that described
Precursor of lithium ionic cell positive material general formula be：NixCoyMnzAld(OH)2+dWherein, 0≤x<1,0≤y<1,0≤z<1,
0.001≤d≤0.1, x+y+z+d=1.
4. the preparation method of anode material for lithium-ion batteries and its presoma according to claim 1, it is characterised in that step
（1）Described in metal salt for sulfate, chlorate, nitrate, one kind in acetate or wherein several.
5. the preparation method of anode material for lithium-ion batteries and its presoma according to claim 1, it is characterised in that step
（1）Described in aluminium salt for aluminum sulfate, aluminum nitrate, one kind in aluminium chloride or wherein several.
6. the preparation method of anode material for lithium-ion batteries and its presoma according to claim 1, it is characterised in that step
（1）Described in alkali be sodium hydroxide, one or both of potassium hydroxide.
7. the preparation method of anode material for lithium-ion batteries and its presoma according to claim 1, it is characterised in that step
（2）In in reaction process to being passed through nitrogen in reaction kettle.
8. the preparation method of anode material for lithium-ion batteries and its presoma according to claim 1, it is characterised in that step
（3）Described in lithium source be lithium carbonate, lithium hydroxide and lithium nitrate in one kind or wherein several.
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| WO2023179048A1 (en) * | 2022-03-25 | 2023-09-28 | 广东邦普循环科技有限公司 | Fluorine-aluminum co-doped lithium cobalt oxide positive electrode material and preparation method therefor |
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