CN103943846B - A kind of preparation method of precursor of lithium ionic cell positive material - Google Patents
A kind of preparation method of precursor of lithium ionic cell positive material Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 14
- 239000000463 material Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000003292 glue Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 239000002019 doping agent Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910003684 NixCoyMnz Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 11
- 239000006104 solid solution Substances 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 7
- 239000010416 ion conductor Substances 0.000 abstract description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 abstract description 2
- 102000004895 Lipoproteins Human genes 0.000 abstract 1
- 108090001030 Lipoproteins Proteins 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 238000000034 method Methods 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
- 239000000126 substance Substances 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
- 229960000935 dehydrated alcohol Drugs 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
- 230000004048 modification Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000975 co-precipitation Methods 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
- 229960004756 ethanol Drugs 0.000 description 1
- 239000008187 granular material Substances 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
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method 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
- 238000005245 sintering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
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- 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
Abstract
The present invention relates to lithium ion battery, refer in particular to the preparation method of a kind of precursor of lithium ionic cell positive material.Configuration multi-element metal saline solution and aqueous slkali；Then, the aqueous slkali of saline solution and stoichiometric proportion excess is stirred the reaction of addition limit below in the effect of ultrasonic external field, controls reaction temperature, control the addition speed of salt, aqueous slkali well；Stand after continuing stirring after completion of the reaction, filter, obtain solid content, be washed with deionized, be dried, i.e. obtain presoma；The precursor powder of doping type is joined in solvent, is placed under ultrasonic external field, after stirring, add metatitanic acid four fourth lipoprotein solution, continue ultrasonic and stirring after, at 50 85 DEG C stirring until formed glue, be dried cooling after surface modify doping type nickel manganese precursor product.The positive electrode material precursor utilizing this invention to prepare has good spherical morphology, it addition, utilize this presoma a step can prepare the doping type solid solution cathode material that surface fast-ionic conductor is modified.
Description
Technical field
The present invention relates to lithium ion battery, refer in particular to the preparation method of a kind of precursor of lithium ionic cell positive material, belong to new energy materials field.
Background technology
Lithium ion battery, because advantages such as its energy density height, good cycle, green non-pollutions, after the eighties of last century appearance nineties, is just developed rapidly, in recent years the fast development of electric automobile, lithium ion battery be also been proposed new requirement.
In recent years, rich lithium solid solution cathode material xLi2MnO3•1-xLiMO2(0 < x < 1, M=Ni, Co, Mn) has higher specific discharge capacity due to it, and cycle performance is preferable, and energy density is high, and becomes the study hotspot of people it is considered to be 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 at present is usually the presoma first preparing nickel cobalt manganese, is then utilizing presoma mixing lithium salts, and sintering prepares positive electrode；Therefore, the composition of nickel cobalt manganese presoma, pattern have decisive meaning to the performance of final synthesis positive electrode.
Presoma the most on sale is usually the hydroxide based on nickel cobalt manganese, and hydroxide owing to can generate water, therefore will certainly produce impact to the performance of positive electrode and pattern during preparing positive electrode；Additionally, also there be not and the report of surface modification modified mutually to nickel cobalt manganese presoma body at present.
Summary of the invention
The present invention devises a kind of doping type nickel cobalt manganese presoma of surface modification and preparation method thereof, and concrete aspect content is as follows:
1 uses ultrasonic external field aid coprecipitation method to prepare doping type nickel cobalt manganese hydroxide precursor, and the molecular formula of described presoma is: NixCoyMnzA1-x-y-z(OH)2；0 < x < 0.6,0≤y≤0.5,0 < z < 0.5,0.95≤x+y+z≤1.
First, with deionized water, the nickel salt weighed according to stoichiometric proportion, cobalt salt, manganese salt and dopant ion salt are dissolved, be configured to the multi-element metal saline solution that total metal ion molar concentration is 0.3-3mol/L, secondly, prepare aqueous slkali；Then, by saline solution and stir addition limit according to the aqueous slkali of stoichiometric proportion excess 20% below in the effect of ultrasonic external field and react, control temperature at 40 DEG C-80 DEG C, control the addition speed of salt, aqueous slkali well, make pH value of reaction system control at 9-12；Stand after continuing stirring after completion of the reaction, filter, obtain solid content, be washed with deionized to alkali metal ion content measured below 0.03%, be dried, i.e. obtain the nickel-cobalt-manganmultielement multielement lithium ion battery positive electrode material presoma of doping type.
Described aqueous slkali is the aqueous solution of sodium hydroxide, potassium hydroxide or Lithium hydrate, and concentration is 1-4mol/L.
The mixing speed of described limit stirring is that 100-600 turns/min.
The described time continuing stirring 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 (C4H9O)4) solution, continue ultrasonic and stirring after, at 50-85 DEG C stirring until formed glue, be dried cooling after surface modify doping type nickel manganese precursor product.
Described solvent is water or ethanol.
The described mixing time stirred is 30-60min；Ultrasonic and stirring the mixing time of described continuation is similarly 30-60min.
Described dry finger is at 150 DEG C of dry 2-3 h.
3, the A ion elements adulterated in step 1 can be Cr3+, Al3+, Mg2+, Ti4+Or Zn2+, 0 < x < 0.6,0≤y≤0.5,0 < z < 0.5,0.95≤x+y+z≤1.
Dopant 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, step 2 adds butyl titanate (Ti (C according to stoichiometric proportion4H9O)4Solution), make the surface coated TiO of presoma2Quality and cladding after the ratio of presoma gross mass be 0.02-0.05:1.
The positive electrode material precursor utilizing this invention to prepare has good spherical morphology, it addition, utilize this presoma a step can prepare the doping type solid solution cathode material that surface fast-ionic conductor is modified.
Accompanying drawing explanation
Presoma scanning electron microscope (SEM) photograph prepared by Fig. 1 present invention, it can be seen that TiO2Cladding Ni0.3Co0.36
Mn0.3Cr0.04(OH)2Presoma pattern is spherical in shape, and surface deposited one layer of nano level granule.
Detailed description of the invention
Embodiment 1: first, dissolves nickel sulfate, cobaltous sulfate, manganese sulfate and chromic nitrate with deionized water, is configured to the multi-element metal saline solution that total metal ion molar concentration is 0.3mol/L, secondly, and the sodium hydroxide solution of compound concentration 1mol/L；Then, reacting under the effect of ultrasonic external field by saline solution and according to the sodium hydroxide solution of stoichiometric proportion excess 20%, control temperature is at 40 DEG C, and mixing speed is 100 turns/min, control the addition speed of salt, aqueous slkali well, make pH value of reaction system control 9；Continuing stirring 0.5 h after completion of the reaction, stand 1 h, filter, obtain solids, be washed with deionized to alkali metal ion content measured below 0.03%, be dried, i.e. obtain the nickel cobalt manganese hydroxide precursor of Cr doping type, molecular formula is: Ni0.3Co0.35Mn0.3Cr0.05(OH)2；The precursor powder of doping type is joined in deionized water, is placed under ultrasonic external field, and be stirred, after 30min, add appropriate metatitanic acid four fourth fat (Ti (C4H9O)4) solution, continue ultrasonic and stir 30 min, at 50 DEG C, stirring forms glue, is then dried 2 h at 150 DEG C, obtains product of the present invention, TiO after cooling2Covering amount is gross mass 2%.Finally by presoma of the present invention and the Li of stoichiometric proportion2CO3Mixing, roasting 12h under the high temperature of 900 DEG C, obtain the miserable miscellaneous type solid solution cathode material that surface is modified.
Embodiment 2: first, dissolves nickel nitrate, cobalt nitrate, manganese nitrate and magnesium nitrate with deionized water, is configured to the multi-element metal saline solution that total metal ion molar concentration is 3 mol/L, secondly, and the potassium hydroxide solution of compound concentration 4mol/L；Then, reacting under the effect of ultrasonic external field by saline solution and according to the potassium hydroxide solution of stoichiometric proportion excess 20%, control temperature is at 50 DEG C, and mixing speed is 600 turns/min, control the addition speed of salt, aqueous slkali well, make pH value of reaction system control 12；Continuing stirring 12 h after completion of the reaction, stand 5 h, filter, obtain solids, be washed with deionized to alkali metal ion content measured below 0.03%, be dried, i.e. obtain the nickel cobalt manganese hydroxide precursor of Mg doping type, molecular formula is: Ni0.3Co0.38Mn0.3Mg0.02(OH)2；The precursor powder of doping type is joined in dehydrated alcohol, is placed under ultrasonic external field, and be stirred, after 60 min, add appropriate metatitanic acid four fourth fat (Ti (C4H9O)4) solution, continue ultrasonic and stir 60 min, at 60 DEG C, stirring forms glue, is then dried 3 h at 150 DEG C, obtains product of the present invention, TiO after cooling2Covering amount is gross mass 5%.Finally by presoma of the present invention and the Li of stoichiometric proportion2CO3Mixing, roasting 12h under the high temperature of 900 DEG C, obtain the miserable miscellaneous type solid solution cathode material that surface is modified.
Embodiment 3: first, dissolves nickel sulfate, cobaltous sulfate, manganese sulfate and chromic nitrate with deionized water, is configured to the multi-element metal saline solution that total metal ion molar concentration is 1 mol/L, secondly, and the lithium hydroxide solution of compound concentration 2 mol/L；Then, reacting under the effect of ultrasonic external field by saline solution and according to the lithium hydroxide solution of stoichiometric proportion excess 20%, control temperature is at 60 DEG C, and mixing speed is 300 turns/min, control the addition speed of salt, aqueous slkali well, make pH value of reaction system control 11；Continuing stirring 4 h after completion of the reaction, stand 2 h, filter, obtain solids, be washed with deionized to alkali metal ion content measured below 0.03%, be dried, i.e. obtain the nickel cobalt manganese hydroxide precursor of Cr doping type, molecular formula is: Ni0.33Co0.35Mn0.3Cr0.02(OH)2；The precursor powder of doping type is joined in deionized water, is placed under ultrasonic external field, and be stirred；After 50min, add appropriate metatitanic acid four fourth fat (Ti (C4H9O)4) solution, continue ultrasonic and stir 50 min, at 70 DEG C, stirring forms glue, is then dried 2.5 h at 150 DEG C, obtains product of the present invention, TiO after cooling2Covering amount is gross mass 3%.Finally by presoma of the present invention and the Li of stoichiometric proportion2CO3Mixing, roasting 12h under the high temperature of 900 DEG C, obtain the miserable miscellaneous type solid solution cathode material that surface is modified.
Embodiment 4: first, dissolves nickel acetate, cobaltous acetate, manganese acetate and aluminum nitrate with deionized water, is configured to the multi-element metal saline solution that total metal ion molar concentration is 0.5 mol/L, secondly, and the sodium hydroxide solution of compound concentration 1mol/L；Then, reacting under the effect of ultrasonic external field by saline solution and according to the sodium hydroxide solution of stoichiometric proportion excess 20%, control temperature is at 70 DEG C, and mixing speed is 300 turns/min, control the addition speed of salt, aqueous slkali well, make pH value of reaction system control 11；Continuing stirring 5 h after completion of the reaction, stand 3 h, filter, obtain solids, be washed with deionized to alkali metal ion content measured below 0.03%, be dried, i.e. obtain the nickel cobalt manganese hydroxide precursor of Al doping type, molecular formula is: Ni0.5Co0.35Mn0.1Al0.05(OH)2；The precursor powder of doping type joins in dehydrated alcohol, is placed under ultrasonic external field, and is stirred, and after 50 min, adds appropriate metatitanic acid four fourth fat (Ti (C4H9O)4) solution, continue ultrasonic and stir 50 min, at 80 DEG C, stirring forms glue, is then dried 2 h at 150 DEG C, obtains product of the present invention, TiO after cooling2Covering amount is gross mass 4%.Finally by presoma of the present invention and the Li of stoichiometric proportion2CO3Mixing, roasting 12h under the high temperature of 900 DEG C, obtain the miserable miscellaneous type solid solution cathode material that surface is modified.
Embodiment 5: first, dissolves nickel sulfate, cobaltous sulfate, manganese sulfate and zinc sulfate with deionized water, is configured to the multi-element metal saline solution that total metal ion molar concentration is 1 mol/L, secondly, and the sodium hydroxide solution of compound concentration 3mol/L；Then, reacting under the effect of ultrasonic external field by saline solution and according to the sodium hydroxide solution of stoichiometric proportion excess 20%, control temperature is at 80 DEG C, and mixing speed is 200 turns/min, control the addition speed of salt, aqueous slkali well, make pH value of reaction system control 11；Continuing stirring 5 h after completion of the reaction, stand 3 h, filter, obtain solids, be washed with deionized to alkali metal ion content measured below 0.03%, be dried, i.e. obtain the nickel cobalt manganese hydroxide precursor of Zn doping type, molecular formula is: Ni0.5Co0.3Mn0.15Zn0.05(OH)2；The precursor powder of doping type is joined in deionized water, is placed under ultrasonic external field, and be stirred, after 50 min, add appropriate metatitanic acid four fourth fat (Ti (C4H9O)4) solution, continue ultrasonic and stir 50 min, at 85 DEG C, stirring forms glue, is then dried 2 h at 150 DEG C, obtains product of the present invention, TiO after cooling2Covering amount is gross mass 2%.Finally by presoma of the present invention and the Li of stoichiometric proportion2CO3Mixing, roasting 12h under the high temperature of 900 DEG C, obtain the miserable miscellaneous type solid solution cathode material that surface is modified.
Table 1 utilizes presoma of the present invention to prepare the chemical property of positive electrode
Listing the presoma utilizing the present invention to prepare in table 1 and prepare the chemical property of solid solution cathode material, as can be seen from the table, the miserable miscellaneous type solid solution cathode material that the surface utilizing presoma of the present invention to prepare is modified has the chemical property of excellence.
Claims (7)
1. a preparation method for precursor of lithium ionic cell positive material, the molecular formula of described presoma is: NixCoyMnzA1-x-y- z(OH)2；0 < x < 0.6,0≤y≤0.5,0 < z < 0.5,0.95≤x+y+z≤1, it is characterised in that comprise the steps:
(1) first, with deionized water, the nickel salt weighed according to stoichiometric proportion, cobalt salt, manganese salt and dopant ion salt are dissolved,
It is configured to multi-element metal saline solution, secondly, prepares aqueous slkali；Then, the aqueous slkali of saline solution and stoichiometric proportion excess is existed
Add while stirring under the effect of ultrasonic external field and react, control temperature at 40 DEG C-80 DEG C, control salt, the adding of aqueous slkali well
Enter speed, make pH value of reaction system control at 9-12；Stand after continuing stirring after completion of the reaction, filter, obtain solid content, use
Deionized water wash to alkali metal ion content measured, is dried, i.e. obtains the nickel-cobalt-manganese multi lithium-ion electric of doping type below 0.03%
Pond positive electrode material precursor；
(2) the nickel-cobalt-manganmultielement multielement lithium ion battery positive electrode material precursor powder of doping type is joined in solvent, be placed in ultrasonic external field
Under, after stirring, add butyl titanate solution, continue ultrasonic and stirring after, at 50-85 DEG C stirring until formed glue
Shape, obtains, after being dried cooling, the precursor of lithium ionic cell positive material that surface is modified；
Described aqueous slkali is the aqueous solution of sodium hydroxide, potassium hydroxide or Lithium hydrate, and concentration is 1-4mol/L；
The A ion elements of doping is Cr3+, Al3+, Mg2+, Ti4+Or Zn2+；Dopant ion salt is nitrate, sulfate or chlorination
Thing；
Described stoichiometric proportion excess refers to stoichiometric proportion excess 20%.
The preparation method of a kind of precursor of lithium ionic cell positive material the most as claimed in claim 1, it is characterised in that: described
Total metal ion molar concentration of multi-element metal saline solution is 0.3-3mol/L.
The preparation method of a kind of precursor of lithium ionic cell positive material the most as claimed in claim 1, it is characterised in that: described
The mixing speed of limit stirring is that 100-600 turns/min；The described time continuing stirring is 0.5-12h；Described time of repose is 1-5
h。
The preparation method of a kind of precursor of lithium ionic cell positive material the most as claimed in claim 1, it is characterised in that: described molten
Agent is water or ethanol.
The preparation method of a kind of precursor of lithium ionic cell positive material the most as claimed in claim 1, it is characterised in that stir described in:
Mixing uniform mixing time is 30-60min；Ultrasonic and stirring the mixing time of described continuation is similarly 30-60min；Described dry
Dry finger is at 150 DEG C of dry 2-3h.
The preparation method of a kind of precursor of lithium ionic cell positive material the most as claimed in claim 1, it is characterised in that: nickel salt,
Cobalt salt and manganese salt are sulfate, nitrate, acetate, oxalates and chloride.
The preparation method of a kind of precursor of lithium ionic cell positive material the most as claimed in claim 1, it is characterised in that: step 2
According to stoichiometric proportion add butyl titanate solution, make the surface coated TiO of presoma2Quality and cladding after presoma
The ratio of gross mass is 0.02-0.05:1.
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