CN104979548B - A kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode - Google Patents
A kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode Download PDFInfo
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- CN104979548B CN104979548B CN201510294611.6A CN201510294611A CN104979548B CN 104979548 B CN104979548 B CN 104979548B CN 201510294611 A CN201510294611 A CN 201510294611A CN 104979548 B CN104979548 B CN 104979548B
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- nickel
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- manganese
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- oxalates
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- 239000002243 precursor Substances 0.000 title claims abstract description 30
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 150000003891 oxalate salts Chemical class 0.000 title abstract description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 manganese, oxalic acid ester Chemical class 0.000 claims abstract description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- IKAUYRPGUOKDFB-UHFFFAOYSA-N cobalt manganese nickel oxalic acid Chemical compound [Mn].[Co].[Ni].C(C(=O)O)(=O)O IKAUYRPGUOKDFB-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 5
- 229940011182 cobalt acetate Drugs 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 5
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 5
- 229940078494 nickel acetate Drugs 0.000 claims description 5
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 3
- 150000003901 oxalic acid esters Chemical class 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004615 ingredient Substances 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000009434 installation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 31
- 229940039748 oxalate Drugs 0.000 description 22
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000002994 raw material Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005049 combustion synthesis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 description 1
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007786 learning performance Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
-
- 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
Abstract
The present invention relates to a kind of preparation methods of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, belong to technical field of energy material.The present invention is existing stoichiometrically to weigh proportioning by nickel, cobalt, the soluble-salt of manganese, oxalic acid ester, organic solvent, is mixed to get mixed solution with water, the oxalates precursor of nickel-cobalt lithium manganate cathode material is then made again.Preparation method of the present invention is simply easily operated, at low cost without special installation.Persursor material ingredient is uniform, and pattern and size tunable, material tap density is big, is conducive to the energy density for improving nickel-cobalt lithium manganate material.
Description
Technical field
The present invention relates to a kind of preparation methods of precursor of lithium ionic cell positive material, and more specifically, the present invention relates to
And a kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, belong to energy and material technology neck
Domain.
Background technology
Lithium ion battery has been quickly grown as novel green battery since appearance.Wherein, positive electrode is to restrict
An important factor for lithium ion battery develops to high-energy density direction.Most potential lithium ion cell positive material currently on the market
Material mainly has cobalt acid lithium, four class of nickle cobalt lithium manganate, LiMn2O4 and LiFePO4.In recent years, the application of nickle cobalt lithium manganate is increasingly wide
It is general, the use of all visible nickle cobalt lithium manganate in lithium ion battery is used in terms of digital communication, power and energy storage.
Nickel-cobalt lithium manganate material combines cobalt acid lithium, the high voltage of three kinds of materials of LiMn2O4 and lithium nickelate, high power capacity it is low at
The development of the advantages of sheet and stability is more and more rapider.The body before mainly passing through different nickle cobalt lithium manganates of nickle cobalt lithium manganate at present
It is sintered and prepares at high temperature after body and lithium salts mixing, method is more.Wherein nickle cobalt lithium manganate precursor：Refer to and prepares nickel cobalt mangaic acid
Important source material nickel cobalt manganese hydroxide, carbonate or the oxalates of lithium, it is especially important to preparing nickle cobalt lithium manganate, electrification
Learning performance has great influence.
State Intellectual Property Office discloses a Publication No. CN 101215011, entitled " nickel cobalt manganese in 2008.7.9
The invention of the coprecipitation-combustion synthesis method of sour lithium ", the disclosure of the invention coprecipitation-combustion synthesis method of nickle cobalt lithium manganate.
(1) using nickel, cobalt, the acetate of manganese or nitrate as transition metal source, ammonium hydroxide is complexing agent, H2C2O4、(NH4)2C2O4、(NH4)2CO3Or NH4HCO3For precipitating reagent, pass through Co deposited synthesis NI-CO-MN compound carbonates or oxalate precursor;It (2) will be upper
The suspension for stating compound carbonate containing NI-CO-MN or oxalates is directly dried, be added lithium nitrate or lithium acetate and a small amount of water or
Ethyl alcohol is tuned into rheology phase;(3) the above-mentioned material in rheology phase is placed in the electric furnace for being heated to 400~600 DEG C and constant temperature
Carry out combustion synthesis reaction;(4) above-mentioned reaction product is obtained into lithium ion cell positive work in 600~1200 DEG C of tempers
Property material LINIXCOYMN1-X-YO2.The invention have it is simple for process, easy to operate, save water and energy, be environmentally protective, synthetic material tool
There are spherical or near-spherical pattern, specific capacity height, good cycle.
By in above-mentioned invention document in the prior art it can be seen that, hydroxide, carbonate, oxalates precursor mesh
The preceding soluble metal salt solution that mainly passes through is under the action of complexing agent ammonium hydroxide, sodium hydroxide or sodium carbonate or sodium oxalate, altogether
It is obtained with homogeneous precipitation.This is a kind of because of synthesis technology relative maturity, becomes industrialized production primary synthetic methods.But at present
Technique synthesis in must all add the pH value that ammonium hydroxide adjusts reaction, while adding the complexing of ammonium hydroxide and metal ion in solution
Its homogeneous precipitation is controlled, prevents the vibration density for reacting the too fast precursor for causing unordered floccule precipitation to cause from spending
It is low.And the pH value in solution carries out being continually changing with reaction, needs to adjust the pH value of reaction in real time to control instead
Answer process, control process is cumbersome, and needs to control the atmosphere of reaction, mainly hydroxide precipitation will under an inert atmosphere into
Row.
Invention content
Present invention seek to address that existing prepare the cumbersome problem of oxalates precursor process control procedure, provide a kind of lithium from
The preparation method of the oxalates precursor of sub- battery nickel-cobalt lithium manganate cathode material, can efficiently control precursor pattern and
Grain size, and technical process is simple, is easy to commercially produce.
In order to achieve the above-mentioned object of the invention, specific technical solution is as follows：
A kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, it is characterised in that：
It comprises the following steps that：
A, nickel, cobalt, the soluble-salt of manganese, oxalic acid ester, organic solvent are stoichiometrically weighed into proportioning, is mixed with water
Obtain mixed solution, nickel in the mixed solution, cobalt, manganese the total concentration of soluble-salt be 0.5-2.5mo1/L, metal from
The mol ratio of son and oxalate is 1:The volume ratio of 1-1.5, water and organic solvent is 1:2-2:1；
B, the step A mixed solutions configured are placed in reaction kettle at a temperature of 45-90 DEG C to be stirred to react 10-24 small
When, then filtration washing, finally fully dry at a temperature of not higher than 130 DEG C, obtains oxalic acid nickel cobalt manganese material, i.e. nickel cobalt manganese
The oxalates precursor of sour lithium anode material, chemical formula NixCoyMn(1-x-y)C2O4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ x+y ＜ 1.
The soluble nickel salt is nickel sulfate, nickel chloride, one kind in nickel acetate or arbitrary ratio to the present invention in step
Example it is a variety of.
The soluble cobalt is cobaltous sulfate, cobalt chloride, one kind in cobalt acetate or arbitrary ratio to the present invention in step
Example it is a variety of.
The soluble manganese salt is manganese sulfate, manganese chloride, one kind in manganese acetate or arbitrary ratio to the present invention in step
Example it is a variety of.
The oxalic acid lipid is dimethyl oxalate or diethy-aceto oxalate to the present invention in step.
The present invention in step the organic solvent be ethyl alcohol, ethylene glycol, methanol, acetone, one kind in isopropanol or
Arbitrary proportion it is a variety of.
The advantageous effects that the present invention is brought：
1, preparation method of the present invention is simply easily operated, at low cost without special installation.Persursor material ingredient is uniform, shape
Looks and size tunable, material tap density is big, is conducive to the energy density for improving nickel-cobalt lithium manganate material.
2, it the present invention provides a kind of oxalates precursor preparation method of nickle cobalt lithium manganate, is mainly characterized by passing through grass
Sour ester hydrolysis gradually discharges oxalate denominationby and is reacted with metal ion, reach homogeneous precipitation growth, without pass through ammonium hydroxide with gold
Belong to the complexing of ion to control reaction process.
3, the present invention prepared by the hydrolysis liquid phase homogeneous precipitations of esters grain size and morphology controllable ingredient it is uniformly careless
Sour nickel cobalt manganese material, chemical formula NixCoyMn(1-x-y)C2O4, pattern can be spherical, spherical, and grain size can control
Between 5um-50um.
Description of the drawings
Fig. 1 is the oxalates precursor XRD spectrum of nickle cobalt lithium manganate prepared by embodiment 6.
Fig. 2 is the oxalates precursor SEM photograph of nickle cobalt lithium manganate prepared by embodiment 6.
Specific implementation mode
Embodiment 1
A kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, including following technique
Step：
A, nickel, cobalt, the soluble-salt of manganese, oxalic acid ester, organic solvent are stoichiometrically weighed into proportioning, is mixed with water
Obtain mixed solution, nickel in the mixed solution, cobalt, manganese the total concentration of soluble-salt be 0.5mo1/L, metal ion with
The mol ratio of oxalate is 1:1, the volume ratio of water and organic solvent is 2:1；
B, the step A mixed solutions configured are placed in reaction kettle and are stirred to react 10 hours at a temperature of 45 DEG C, so
Filtration washing afterwards, it is finally fully dry at a temperature of not higher than 130 DEG C, obtain oxalic acid nickel cobalt manganese material, i.e. nickle cobalt lithium manganate
The oxalates precursor of positive electrode, chemical formula NixCoyMn(1-x-y)C2O4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ x+y ＜ 1.
Embodiment 2
A kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, including following technique
Step：
A, nickel, cobalt, the soluble-salt of manganese, oxalic acid ester, organic solvent are stoichiometrically weighed into proportioning, is mixed with water
Obtain mixed solution, nickel in the mixed solution, cobalt, manganese the total concentration of soluble-salt be 2.5mo1/L, metal ion with
The mol ratio of oxalate is 1:1.5, the volume ratio of water and organic solvent is 1:2；
B, the step A mixed solutions configured are placed in reaction kettle and are stirred to react 24 hours at a temperature of 90 DEG C, so
Filtration washing afterwards, it is finally fully dry at a temperature of not higher than 130 DEG C, obtain oxalic acid nickel cobalt manganese material, i.e. nickle cobalt lithium manganate
The oxalates precursor of positive electrode, chemical formula NixCoyMn(1-x-y)C2O4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ x+y ＜ 1.
Embodiment 3
A kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, including following technique
Step：
A, nickel, cobalt, the soluble-salt of manganese, oxalic acid ester, organic solvent are stoichiometrically weighed into proportioning, is mixed with water
Obtain mixed solution, nickel in the mixed solution, cobalt, manganese the total concentration of soluble-salt be 1.5mo1/L, metal ion with
The mol ratio of oxalate is 1:1.25, the volume ratio of water and organic solvent is 1:1.25；
B, the step A mixed solutions configured are placed in reaction kettle and are stirred to react 17 hours at a temperature of 67.5 DEG C,
Then filtration washing, it is finally fully dry at a temperature of not higher than 130 DEG C, obtain oxalic acid nickel cobalt manganese material, i.e. nickel cobalt mangaic acid
The oxalates precursor of lithium anode material, chemical formula NixCoyMn(1-x-y)C2O4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ x+y ＜ 1.
Embodiment 4
A kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, including following technique
Step：
A, nickel, cobalt, the soluble-salt of manganese, oxalic acid ester, organic solvent are stoichiometrically weighed into proportioning, is mixed with water
Obtain mixed solution, nickel in the mixed solution, cobalt, manganese the total concentration of soluble-salt be 2.1mo1/L, metal ion with
The mol ratio of oxalate is 1:1.1, the volume ratio of water and organic solvent is 1:1.7；
B, the step A mixed solutions configured are placed in reaction kettle and are stirred to react 12 hours at a temperature of 85 DEG C, so
Filtration washing afterwards, it is finally fully dry at a temperature of not higher than 130 DEG C, obtain oxalic acid nickel cobalt manganese material, i.e. nickle cobalt lithium manganate
The oxalates precursor of positive electrode, chemical formula NixCoyMn(1-x-y)C2O4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ x+y ＜ 1.
Embodiment 5
On the basis of embodiment 1-4：
Preferably, the soluble nickel salt is nickel sulfate, nickel chloride, one kind in nickel acetate or arbitrary in step
Ratio it is a variety of.
Preferably, the soluble cobalt is cobaltous sulfate, cobalt chloride, one kind in cobalt acetate or arbitrary in step
Ratio it is a variety of.
Preferably, the soluble manganese salt is manganese sulfate, manganese chloride, one kind in manganese acetate or arbitrary in step
Ratio it is a variety of.
Preferably, the oxalic acid lipid is dimethyl oxalate or diethy-aceto oxalate in step.
Preferably, the organic solvent is one kind in ethyl alcohol, ethylene glycol, methanol, acetone, isopropanol in step
Or arbitrary proportion is a variety of.
Embodiment 6
Respectively using nickel sulfate, manganese sulfate, cobaltous sulfate as raw material, nickel, cobalt, manganese molar ratio 1:1:1 prepares solution, control
The total concentration for preparing nickel cobalt manganese in the mixed solution of the nickel cobalt manganese salt of system is 1mol/L.According to mole of metal ion and oxalate
Proportioning is 1:1.2 add diethy-aceto oxalate into solution, are 2 according to water and organic solvent volume ratio:1 adds second two into solution
Alcohol.The solution configured is placed in reaction kettle after being stirred to react 16 hours at a temperature of 75 DEG C after filtration washing at 90 DEG C
At a temperature of it is fully dry after obtain oxalic acid nickel cobalt manganese material；
Fig. 1 gives the oxalates precursor XRD spectrum of prepared nickle cobalt lithium manganate, and Fig. 2 gives prepared nickel cobalt manganese
The oxalates precursor SEM photograph of sour lithium, material morphology are spherical shape, and grain size is between 5um-15um.
Embodiment 7
Respectively using nickel sulfate, manganese sulfate, cobaltous sulfate as raw material, nickel, cobalt, manganese molar ratio 6:2:2 prepare solution, control
The total concentration for preparing nickel cobalt manganese in the mixed solution of the nickel cobalt manganese salt of system is 0.5mol/L.According to rubbing for metal ion and oxalate
Your proportioning is 1:1 adds diethy-aceto oxalate into solution, is 1 according to water and organic solvent volume ratio:1 adds second into solution
Alcohol.The solution configured is placed in reaction kettle after being stirred to react 10 hours at a temperature of 90 DEG C after filtration washing at 120 DEG C
At a temperature of it is fully dry after obtain oxalic acid nickel cobalt manganese material.
Embodiment 8
Respectively using nickel chloride, manganese chloride, cobalt chloride as raw material, nickel, cobalt, manganese molar ratio 5:2:3 prepare solution, control
The total concentration for preparing nickel cobalt manganese in the mixed solution of the nickel cobalt manganese salt of system is 2.5mol/L.According to rubbing for metal ion and oxalate
Your proportioning is 1:1.5 add dimethyl oxalate into solution, are 1 according to water and organic solvent volume ratio:2 add third into solution
Ketone.The solution configured is placed in reaction kettle after being stirred to react 24 hours at a temperature of 45 DEG C after filtration washing at 110 DEG C
At a temperature of it is fully dry after obtain oxalic acid nickel cobalt manganese material.
Embodiment 9
Respectively using nickel chloride, manganese chloride, cobalt chloride as raw material, nickel, cobalt, manganese molar ratio 6:2:2 prepare solution, control
The total concentration for preparing nickel cobalt manganese in the mixed solution of the nickel cobalt manganese salt of system is 1.5mol/L.According to rubbing for metal ion and oxalate
Your proportioning is 1:1.4 add diethy-aceto oxalate into solution, are 1 according to water and organic solvent volume ratio:1 adds second into solution
Glycol.The solution configured is placed in reaction kettle after being stirred to react 16 hours at a temperature of 80 DEG C after filtration washing 100
Oxalic acid nickel cobalt manganese material is obtained after fully being dried at a temperature of DEG C.
Embodiment 10
Respectively using nickel acetate, manganese acetate, cobalt acetate as raw material, nickel, cobalt, manganese molar ratio 1:1:1 prepares solution, control
The total concentration for preparing nickel cobalt manganese in the mixed solution of the nickel cobalt manganese salt of system is 1.5mol/L.According to rubbing for metal ion and oxalate
Your proportioning is 1:1.1 add diethy-aceto oxalate into solution, are 2 according to water and organic solvent volume ratio:1 adds second into solution
Alcohol.The solution configured is placed in reaction kettle after being stirred to react 20 hours at a temperature of 75 DEG C after filtration washing at 100 DEG C
At a temperature of it is fully dry after obtain oxalic acid nickel cobalt manganese material.
Embodiment 11
Respectively using nickel acetate, manganese acetate, cobalt acetate as raw material, nickel, cobalt, manganese molar ratio 6:2:2 prepare solution, control
The total concentration for preparing nickel cobalt manganese in the mixed solution of the nickel cobalt manganese salt of system is 1.5mol/L.According to rubbing for metal ion and oxalate
Your proportioning is 1:1.2 add diethy-aceto oxalate into solution, are 1 according to water and organic solvent volume ratio:1.5 add into solution
Ethylene glycol.The solution configured is placed in reaction kettle after being stirred to react 16 hours at a temperature of 80 DEG C after filtration washing 90
Oxalic acid nickel cobalt manganese material is obtained after fully being dried at a temperature of DEG C.
Embodiment 12
Respectively using nickel sulfate, manganese sulfate, cobaltous sulfate as raw material, nickel, cobalt, manganese molar ratio 1:1:1 prepares solution, control
The total concentration for preparing nickel cobalt manganese in the mixed solution of the nickel cobalt manganese salt of system is 2mol/L.According to mole of metal ion and oxalate
Proportioning is 1:1.3 add diethy-aceto oxalate into solution, are 1 according to water and organic solvent volume ratio:1 adds second two into solution
Alcohol.The solution configured is placed in reaction kettle after being stirred to react 22 hours at a temperature of 70 DEG C after filtration washing at 100 DEG C
At a temperature of it is fully dry after obtain oxalic acid nickel cobalt manganese material.
Claims (1)
1. a kind of preparation method of the oxalates precursor of lithium ion battery nickle cobalt lithium manganate positive electrode, it is characterised in that：Packet
Include following processing step：
A, nickel, cobalt, the soluble-salt of manganese, oxalic acid ester, organic solvent are stoichiometrically weighed into proportioning, is mixed to get with water
Mixed solution, nickel in the mixed solution, cobalt, manganese the total concentration of soluble-salt be 2.1mo1/L, metal ion and oxalic acid
The mol ratio of root is 1:1.1, the volume ratio of water and organic solvent is 1:1.7；The soluble nickel salt is nickel sulfate, chlorine
Change a variety of of nickel, one kind in nickel acetate or arbitrary proportion；The soluble cobalt is in cobaltous sulfate, cobalt chloride, cobalt acetate
One kind or arbitrary proportion it is a variety of；The oxalic acid lipid is dimethyl oxalate or diethy-aceto oxalate；Described is organic molten
Agent is a variety of of ethyl alcohol, ethylene glycol, methanol, acetone, one kind in isopropanol or arbitrary proportion；
B, the step A mixed solutions configured are placed in reaction kettle and are stirred to react 12 hours at a temperature of 85 DEG C, then mistake
Filter washing, it is finally fully dry at a temperature of not higher than 130 DEG C, obtain oxalic acid nickel cobalt manganese material, i.e. nickle cobalt lithium manganate anode
The oxalates precursor of material, chemical formula NixCoyMn(1-x-y)C2O4, 0 ＜ x ＜, 1,0 ＜ y ＜, 1,0 ＜ x+y ＜ 1.
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