CN103943846A - Preparation method of lithium ion battery positive-electrode material precursor - Google Patents
Preparation method of lithium ion battery positive-electrode material precursor Download PDFInfo
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- CN103943846A CN103943846A CN201410156530.5A CN201410156530A CN103943846A CN 103943846 A CN103943846 A CN 103943846A CN 201410156530 A CN201410156530 A CN 201410156530A CN 103943846 A CN103943846 A CN 103943846A
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- cell positive
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- 239000002243 precursor Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 6
- 239000007774 positive electrode material Substances 0.000 title abstract 4
- 238000003756 stirring Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 5
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 238000009938 salting Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- -1 ion salt Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 239000010416 ion conductor Substances 0.000 abstract description 2
- 239000012670 alkaline solution Substances 0.000 abstract 3
- 239000011259 mixed solution Substances 0.000 abstract 3
- 239000012266 salt solution Substances 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 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 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 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
- 230000008021 deposition Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229940071125 manganese acetate Drugs 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 239000002245 particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a lithium ion battery and particularly relates to a preparation method of a lithium ion battery positive-electrode material precursor. The preparation method comprises the following steps: preparing a multi-element metal salt solution and an alkaline solution; then, in the presence of an ultrasonic out-field, adding the multi-element metal salt solution and the excess alkaline solution in a stoichiometric ratio during stirring, and reacting, wherein the reaction temperature and the adding speed of the salt solution and the alkaline solution are well controlled; after reaction, continuously stirring, then standing and filtering to obtain a solid substance; washing the solid substance with deionized water, and drying the washed substance to obtain a precursor I; adding doped precursor powder in a solvent to obtain a mixture, placing the mixture in the ultrasonic out-field, evenly stirring the mixture, adding a tetrabutyl titanate solution to obtain a mixed solution, performing ultrasonic treatment and stirring continuously on the mixed solution, stirring the mixed solution at the temperature of 50-85 DEG C until gel forms, and drying and cooling the gel to obtain a doped nickel-manganese precursor product with a modified surface. The positive-electrode material precursor prepared by adopting the method has the good spherical morphology; besides, by virtue of the precursor, a doped solid solution positive-electrode material with surface modified by fast ionic conductors can be further prepared.
Description
Technical field
The present invention relates to lithium ion battery, refer in particular to a kind of preparation method of precursor of lithium ionic cell positive material, belong to new energy materials field.
Background technology
Lithium ion battery is because the advantages such as its energy density is high, good cycle, green non-pollution, after the eighties of last century appearance nineties, are just developed rapidly, and the fast development of electric automobile in recent years, has proposed again new requirement to lithium ion battery.
In recent years, rich lithium solid solution cathode material xLi
2mnO
31-xLiMO
2(0<x<1, M=Ni, Co, Mn) because it has higher specific discharge capacity, cycle performance is better, and energy density is high, form the study hotspot for people, be considered to the first-selected positive electrode of New Generation of Electric Vehicle lithium-ion-power cell.
The method of the rich lithium solid solution cathode material of preparation is generally first to prepare the presoma of nickel cobalt manganese at present, is then utilizing presoma mixing lithium salts, and sintering is prepared positive electrode; Therefore, the composition of nickel cobalt manganese presoma, pattern have decisive meaning to the performance of final synthetic positive electrode.
In the market presoma on sale be generally hydroxide taking nickel cobalt manganese as main, hydroxide, preparing in positive electrode process because meeting generates water, therefore will certainly exert an influence to the performance of positive electrode and pattern; In addition also there is not, the report of pair nickel cobalt manganese presoma body phase modification and finishing at present.
Summary of the invention
The present invention has designed doping type nickel cobalt manganese presoma of a kind of finishing and preparation method thereof, and concrete aspects is as follows:
1 adopts the auxiliary coprecipitation of ultrasonic external field to prepare doping type nickel cobalt manganese hydroxide presoma, and the molecular formula of described presoma is: Ni
xco
ymn
za
1-x-y-z(OH)
2; 0<x<0.6,0≤y≤0.5,0<z<0.5,0.95≤x+y+z≤1.
First, by the nickel salt weighing according to stoichiometric proportion, cobalt salt, manganese salt and the dissolving of doping ion salt, be configured to the multi-element metal salting liquid that total metal ion molar concentration is 0.3-3mol/L with deionized water, secondly, preparation aqueous slkali; Then, stir and add limit to react below in the effect of ultrasonic external field by salting liquid and according to the aqueous slkali of stoichiometric proportion excessive 20%, control temperature at 40 DEG C-80 DEG C, control the speed that adds of salt, aqueous slkali well, make pH value of reaction system be controlled at 9-12; After continuing after completion of the reaction to stir, leave standstill, filter, obtain solid content, wash to alkali metal ion content measured below 0.03% with deionized water, dry, obtain the nickel-cobalt-manganese multi precursor of lithium ionic cell positive material of doping type.
Described aqueous slkali is the aqueous solution of NaOH, potassium hydroxide or lithium hydroxide, and concentration is 1-4mol/L.
The mixing speed that stir on described limit is turn/min of 100-600.
The time that described continuation is stirred is 0.5-12 h.
Described time of repose is 1-5 h.
2, the precursor powder of doping type is joined in solvent, be placed under ultrasonic external field, after stirring, add metatitanic acid four fourth fat (Ti (C
4h
9o)
4) solution, continue ultrasonic and stir after, at 50-85 DEG C, stir until form gluey, dry after cooling the doping type nickel manganese presoma product of finishing.
Described solvent is water or ethanol.
The described mixing time stirring is 30-60min; Described continuation mixing time ultrasonic and that stir is similarly 30-60min.
Described dry finger is at 150 DEG C of dry 2-3 h.
3, in step 1, the A ion elements of doping can be Cr
3+, Al
3+, Mg
2+, Ti
4+or Zn
2+, 0<x<0.6,0≤y≤0.5,0<z<0.5,0.95≤x+y+z≤1.
Doping ion salt is nitrate, sulfate or chloride.
Nickel salt, cobalt salt and manganese salt are sulfate, nitrate, acetate, oxalates and chloride; It is chosen as routine techniques means.
4, in step 2, add butyl titanate (Ti (C according to stoichiometric proportion
4h
9o)
4solution), make the surface coated TiO of presoma
2quality and coated after the ratio of presoma gross mass be 0.02-0.05:1.
Utilize positive electrode presoma prepared by this invention to there is good spherical morphology, in addition, utilize this presoma a step to prepare the doping type solid solution cathode material that surperficial fast-ionic conductor is modified.
Brief description of the drawings
Presoma scanning electron microscope (SEM) photograph prepared by Fig. 1 the present invention, as can be seen from the figure, TiO
2coated Ni
0.3co
0.36
Mn
0.3cr
0.04(OH)
2presoma pattern is spherical in shape, surface deposition the nano level particle of one deck.
Embodiment
Embodiment 1: first, by nickelous sulfate, cobaltous sulfate, manganese sulfate and chromic nitrate dissolving, be configured to the multi-element metal salting liquid that total metal ion molar concentration is 0.3mol/L with deionized water, secondly, the sodium hydroxide solution of compound concentration 1mol/L; Then, react under the effect of ultrasonic external field by salting liquid and according to the sodium hydroxide solution of stoichiometric proportion excessive 20%, control temperature at 40 DEG C, mixing speed is 100 turn/min, control the speed that adds of salt, aqueous slkali well, make pH value of reaction system be controlled at 9; Continue after completion of the reaction to stir 0.5 h, leave standstill 1 h, filter, obtain solids, wash to alkali metal ion content measured below 0.03% with deionized water, dry, obtain the nickel cobalt manganese hydroxide presoma of Cr doping type, molecular formula is: Ni
0.3co
0.35mn
0.3cr
0.05(OH)
2; The precursor powder of doping type is joined in deionized water, be placed under ultrasonic external field, and stir, after 30min, add appropriate metatitanic acid four fourth fat (Ti (C
4h
9o)
4) solution, continue ultrasonic and stir 30 min, at 50 DEG C, stir form gluey, then at 150 DEG C of dry 2 h, after cooling product of the present invention, TiO
2covering amount be gross mass 2%.Finally by the Li of presoma of the present invention and stoichiometric proportion
2cO
3mix, roasting 12h under the high temperature of 900 DEG C, obtains the miserable assorted type solid solution cathode material of finishing.
Embodiment 2: first, by nickel nitrate, cobalt nitrate, manganese nitrate and magnesium nitrate dissolving, be configured to the multi-element metal salting liquid that total metal ion molar concentration is 3 mol/L with deionized water, secondly, the potassium hydroxide solution of compound concentration 4mol/L; Then, react under the effect of ultrasonic external field by salting liquid and according to the potassium hydroxide solution of stoichiometric proportion excessive 20%, control temperature at 50 DEG C, mixing speed is 600 turn/min, control the speed that adds of salt, aqueous slkali well, make pH value of reaction system be controlled at 12; Continue after completion of the reaction to stir 12 h, leave standstill 5 h, filter, obtain solids, wash to alkali metal ion content measured below 0.03% with deionized water, dry, obtain the nickel cobalt manganese hydroxide presoma of Mg doping type, molecular formula is: Ni
0.3co
0.38mn
0.3mg
0.02(OH)
2; The precursor powder of doping type is joined in absolute ethyl alcohol, be placed under ultrasonic external field, and stir, after 60 min, add appropriate metatitanic acid four fourth fat (Ti (C
4h
9o)
4) solution, continue ultrasonic and stir 60 min, at 60 DEG C, stir form gluey, then at 150 DEG C of dry 3 h, after cooling product of the present invention, TiO
2covering amount be gross mass 5%.Finally by the Li of presoma of the present invention and stoichiometric proportion
2cO
3mix, roasting 12h under the high temperature of 900 DEG C, obtains the miserable assorted type solid solution cathode material of finishing.
Embodiment 3: first, by nickelous sulfate, cobaltous sulfate, manganese sulfate and chromic nitrate dissolving, be configured to the multi-element metal salting liquid that total metal ion molar concentration is 1 mol/L with deionized water, secondly, the lithium hydroxide solution of compound concentration 2 mol/L; Then, react under the effect of ultrasonic external field by salting liquid and according to the lithium hydroxide solution of stoichiometric proportion excessive 20%, control temperature at 60 DEG C, mixing speed is 300 turn/min, control the speed that adds of salt, aqueous slkali well, make pH value of reaction system be controlled at 11; Continue after completion of the reaction to stir 4 h, leave standstill 2 h, filter, obtain solids, wash to alkali metal ion content measured below 0.03% with deionized water, dry, obtain the nickel cobalt manganese hydroxide presoma of Cr doping type, molecular formula is: Ni
0.33co
0.35mn
0.3cr
0.02(OH)
2; The precursor powder of doping type is joined in deionized water, be placed under ultrasonic external field, and stir; After 50min, add appropriate metatitanic acid four fourth fat (Ti (C
4h
9o)
4) solution, continue ultrasonic and stir 50 min, at 70 DEG C, stir form gluey, then at 150 DEG C of dry 2.5 h, after cooling product of the present invention, TiO
2covering amount be gross mass 3%.Finally by the Li of presoma of the present invention and stoichiometric proportion
2cO
3mix, roasting 12h under the high temperature of 900 DEG C, obtains the miserable assorted type solid solution cathode material of finishing.
Embodiment 4: first, by nickel acetate, cobalt acetate, manganese acetate and aluminum nitrate dissolving, be configured to the multi-element metal salting liquid that total metal ion molar concentration is 0.5 mol/L with deionized water, secondly, the sodium hydroxide solution of compound concentration 1mol/L; Then, react under the effect of ultrasonic external field by salting liquid and according to the sodium hydroxide solution of stoichiometric proportion excessive 20%, control temperature at 70 DEG C, mixing speed is 300 turn/min, control the speed that adds of salt, aqueous slkali well, make pH value of reaction system be controlled at 11; Continue after completion of the reaction to stir 5 h, leave standstill 3 h, filter, obtain solids, wash to alkali metal ion content measured below 0.03% with deionized water, dry, obtain the nickel cobalt manganese hydroxide presoma of Al doping type, molecular formula is: Ni
0.5co
0.35mn
0.1al
0.05(OH)
2; The precursor powder of doping type joins in absolute ethyl alcohol, is placed under ultrasonic external field, and stirs, and after 50 min, adds appropriate metatitanic acid four fourth fat (Ti (C
4h
9o)
4) solution, continue ultrasonic and stir 50 min, at 80 DEG C, stir form gluey, then at 150 DEG C of dry 2 h, after cooling product of the present invention, TiO
2covering amount be gross mass 4%.Finally by the Li of presoma of the present invention and stoichiometric proportion
2cO
3mix, roasting 12h under the high temperature of 900 DEG C, obtains the miserable assorted type solid solution cathode material of finishing.
Embodiment 5: first, by nickelous sulfate, cobaltous sulfate, manganese sulfate and zinc sulfate dissolving, be configured to the multi-element metal salting liquid that total metal ion molar concentration is 1 mol/L with deionized water, secondly, the sodium hydroxide solution of compound concentration 3mol/L; Then, react under the effect of ultrasonic external field by salting liquid and according to the sodium hydroxide solution of stoichiometric proportion excessive 20%, control temperature at 80 DEG C, mixing speed is 200 turn/min, control the speed that adds of salt, aqueous slkali well, make pH value of reaction system be controlled at 11; Continue after completion of the reaction to stir 5 h, leave standstill 3 h, filter, obtain solids, wash to alkali metal ion content measured below 0.03% with deionized water, dry, obtain the nickel cobalt manganese hydroxide presoma of Zn doping type, molecular formula is: Ni
0.5co
0.3mn
0.15zn
0.05(OH)
2; The precursor powder of doping type is joined in deionized water, be placed under ultrasonic external field, and stir, after 50 min, add appropriate metatitanic acid four fourth fat (Ti (C
4h
9o)
4) solution, continue ultrasonic and stir 50 min, at 85 DEG C, stir form gluey, then at 150 DEG C of dry 2 h, after cooling product of the present invention, TiO
2covering amount be gross mass 2%.Finally by the Li of presoma of the present invention and stoichiometric proportion
2cO
3mix, roasting 12h under the high temperature of 900 DEG C, obtains the miserable assorted type solid solution cathode material of finishing.
Table 1 utilizes presoma of the present invention to prepare the chemical property of positive electrode
In table 1, list the chemical property that utilizes presoma prepared by the present invention to prepare solid solution cathode material, as can be seen from the table, utilized the miserable assorted type solid solution cathode material of finishing prepared by presoma of the present invention to there is excellent chemical property.
Claims (9)
1. a preparation method for precursor of lithium ionic cell positive material, the molecular formula of described presoma is: Ni
xco
ymn
za
1-x-y-z(OH)
2; 0<x<0.6,0≤y≤0.5,0<z<0.5,0.95≤x+y+z≤1, is characterized in that comprising the steps:
(1) first, by the nickel salt weighing according to stoichiometric proportion, cobalt salt, manganese salt and the dissolving of doping ion salt, be configured to multi-element metal salting liquid with deionized water, secondly, preparation aqueous slkali; Then, salting liquid and the excessive aqueous slkali of stoichiometric proportion are stirred and add limit to react below in the effect of ultrasonic external field, control temperature at 40 DEG C-80 DEG C, control the speed that adds of salt, aqueous slkali well, make pH value of reaction system be controlled at 9-12; After continuing after completion of the reaction to stir, leave standstill, filter, obtain solid content, wash to alkali metal ion content measured below 0.03% with deionized water, dry, obtain the nickel-cobalt-manganese multi precursor of lithium ionic cell positive material of doping type;
(2) precursor powder of doping type is joined in solvent, be placed under ultrasonic external field, after stirring, add metatitanic acid four fourth fat (Ti (C
4h
9o)
4) solution, continue ultrasonic and stir after, at 50-85 DEG C, stir until form gluey, dry after cooling the doping type nickel manganese presoma product of finishing.
2. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: total metal ion molar concentration of described multi-element metal salting liquid is 0.3-3mol/L; The excessive finger stoichiometric proportion excessive 20% of described stoichiometric proportion.
3. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: described aqueous slkali is the aqueous solution of NaOH, potassium hydroxide or lithium hydroxide, and concentration is 1-4mol/L.
4. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: the mixing speed that stir on described limit is turn/min of 100-600; The time that described continuation is stirred is 0.5-12 h; Described time of repose is 1-5 h.
5. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: described solvent is water or ethanol.
6. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: described in the mixing time that stirs be 30-60min; Described continuation mixing time ultrasonic and that stir is similarly 30-60min; Described dry finger is at 150 DEG C of dry 2-3 h.
7. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: in step 1, the A ion elements of doping is Cr
3+, Al
3+, Mg
2+, Ti
4+or Zn
2+; Doping ion salt is nitrate, sulfate or chloride.
8. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: nickel salt, cobalt salt and manganese salt are sulfate, nitrate, acetate, oxalates and chloride.
9. the preparation method of a kind of precursor of lithium ionic cell positive material as claimed in claim 1, is characterized in that: in step 2, add butyl titanate (Ti (C according to stoichiometric proportion
4h
9o)
4solution), make the surface coated TiO of presoma
2quality and coated after the ratio of presoma gross mass be 0.02-0.05:1.
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| CN104966811A (en) * | 2015-06-05 | 2015-10-07 | 苏州珍展科技材料有限公司 | Positive electrode precursor material of lithium ion battery and preparation method thereof |
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