CN103715418A - Preparation method for spherical cobaltosic oxide - Google Patents
Preparation method for spherical cobaltosic oxide Download PDFInfo
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- CN103715418A CN103715418A CN201210368566.0A CN201210368566A CN103715418A CN 103715418 A CN103715418 A CN 103715418A CN 201210368566 A CN201210368566 A CN 201210368566A CN 103715418 A CN103715418 A CN 103715418A
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- cobaltous
- spherical cobaltic
- cobaltous oxide
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- -1 subsulfate Chemical compound 0.000 claims 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 2
- 238000001354 calcination Methods 0.000 claims 2
- 239000007795 chemical reaction product Substances 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 229910052772 Samarium Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910052788 barium Inorganic materials 0.000 claims 1
- 150000004675 formic acid derivatives Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000004767 nitrides Chemical class 0.000 claims 1
- 150000003891 oxalate salts Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 13
- 150000001868 cobalt Chemical class 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 229910021654 trace metal Inorganic materials 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron 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
- 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 invention discloses a preparation method for spherical cobaltosic oxide. The preparation method comprises the steps of mixing a cobalt salt with other trace metal elements; adding a precipitator and an oxidant in a flowing manner to obtain a synthetic product; and subjecting the synthetic product to solid-liquid separation, washing and sintering to obtain the spherical cobaltosic oxide material. The method disclosed by the invention is simple in process and convenient for operation; and the obtained product is uniform in distribution of doping elements, narrow in particle size distribution, good in degree of sphericity, and high in density.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, be specifically related to a kind of preparation method of spherical cobaltic-cobaltous oxide.
Background technology
Lithium ion battery has been widely used in the small type mobile devices fields such as mobile phone, panel computer at present.And LiCoO
2it is most widely used lithium electricity positive electrode in this field, the cobalt acid lithium material of pure phase in cyclic process owing to generally only having the embedding of 50% lithium ion and deviating from, once go beyond the limit, overcharge, to make structure undergo phase transition avalanche, lattice oxygen loss,, also there is potential safety hazard in the decay fast that can cause circulating.
In order to overcome the defect of traditional cobalt acid lithium material, people improve its structure by doped metal ion, and these metallic elements, in the layer structure of stable crystal, suppress the irreversible transition occurring in the de-embedding process of lithium ion; Improve width between material layer, be beneficial to the diffusion of lithium ion and the aspects such as discharge voltage that improve material, there is significant effect.
At present, doping majority for cobalt acid lithium material concentrates on dry method aspect, as CN201110314401.0 and the disclosed technical scheme of CN200910264194.5, are all methods of doping type cobalt acid lithium that cobaltosic oxide, metal oxide, lithium carbonate mixed sintering are obtained, but in these class methods, very difficult realization of doped chemical is dispersed in lattice structure inside.
And aspect wet method, cobalt carbonate that patent CN20121011485.5 discloses is magnesium-doped, in the technique of aluminium, titanium, need to adopt carbonic hydroammonium as complexing and precipitation reagent, gained cobalt carbonate needs high-temperature calcination, and fragmentation makes cobaltosic oxide, energy consumption is high, simultaneously to environment; In the preparation technology of the cobaltosic oxide of introducing in CN200810110753.2 owing to adding ammoniacal liquor as complexing agent, can be to environment.
Therefore, need a kind of cost low, pollution-free, be convenient to suitability for industrialized production, can realize doped chemical dispersed, the method for good sphericity is prepared high performance spherical cobaltic-cobaltous oxide.
Summary of the invention
The object of the invention is to provide to this area a kind of preparation method of spherical cobaltic-cobaltous oxide, the cobalt acid lithium that the cobaltosic oxide of preparation can make to produce has the feature of high voltage, good cycle, and this product doped chemical is evenly distributed, good sphericity, density is high, and technique is simple, easy to operate, easily realize suitability for industrialized production, and production process is pollution-free, environmental friendliness.
The object of the invention is to be achieved through the following technical solutions:
A kind of preparation method of spherical cobaltic-cobaltous oxide mainly comprises the following steps:
(1) raw material preparation
1. in pure water according to mol ratio (1-a-b): a:b(0 < a≤0.05,0≤b≤0.05) add the material that contains cobalt, M, L, be mixed with the mixing material that concentration is 0.5 ~ 3.5mol/L, note keeping in liquid feed liquor process in stirring;
2. compound concentration is the precipitant solution of 0.5 ~ 15 mol/L;
3. select suitable oxidant.
(2) course of reaction
4. the mode that adopts and flow passes into mixing material, precipitant solution, oxidant in reactor simultaneously, under agitation makes three react, and pH value 7 ~ 12, reaction temperature are 40 ~ 90 ℃, obtain synthetic product.
5. synthetic product obtains filter cake through Separation of Solid and Liquid, washing, and then filter cake is calcined 2 ~ 20h and obtained (Co under 400 ~ 800 ℃ of conditions
(1-a-b)m
al
b)
3o
4powder.
In above-mentioned preparation method, step 1. described cobalt salt with a kind of in cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate or cobaltous formate or wherein several forms exist.
In above-mentioned preparation method, the M of step described in 1. can be a kind of or wherein several in Ni, Mn, Cr, Fe, Mg, Ca, Ti, Zr, Sr, Ba, Sm, Al, Y or Zn.
In above-mentioned preparation method, the L of step described in 1. can be a kind of or wherein several in V, Nb, Ta, B, Ti, Sm, Zr, Mo, Hf or W.
In above-mentioned preparation method, the OH that the precipitation reagent of step described in 2. provides precipitation by metallic ion to need
-, the precipitation reagent generally adopting can be a kind of in ammoniacal liquor, NaOH, potassium hydroxide, lithium hydroxide or several mixture wherein.
In above-mentioned preparation method, the oxidant of step described in 3. can be a kind of in oxygen, air, hydrogen peroxide, clorox, sodium perchlorate, sodium peroxydisulfate, ozone, chlorine, sodium peroxide or several mixture wherein.
In above-mentioned preparation method, step
the middle mol ratio that need control precipitation reagent and the total salt of metal is 1.5 ~ 2.5.
In above-mentioned preparation method, step
the middle mol ratio that need control oxidant and the total salt of metal is 0.2 ~ 4.
According to the prepared spherical cobaltic-cobaltous oxide of the preparation method of above a kind of spherical cobaltic-cobaltous oxide, chemical formula can be expressed as (Co
(1-a-b)m
al
b)
3o
4(0 ﹤ a≤0.05,0≤b≤0.05), its D
50=5 ~ 25 um, AD>=1.0g/cm
3.
The preparation method of a kind of spherical cobaltic-cobaltous oxide of the present invention, pass through doped metallic elements, the cobaltosic oxide of preparation, have that doped chemical is evenly distributed, density is high, good sphericity, the cobalt acid lithium overcharging resisting of preparation, circulation volume conservation rate advantages of higher, and technical flow design is smooth and easy, environmental friendliness, production process is pollution-free, is suitable for industrialization.
Accompanying drawing explanation
Fig. 1 is the spherical cobaltic-cobaltous oxide SEM photo making in embodiment 4;
Fig. 2 is the XRD collection of illustrative plates of the spherical cobaltic-cobaltous oxide that makes in embodiment 4;
Fig. 3 is cobalt acid lithium capacity circulating curve prepared by the spherical cobaltic-cobaltous oxide that makes in embodiment 4.
specific implementation method
Illustrate below by way of embodiments and drawings embodiments of the present invention.
embodiment 1
A preparation method for spherical cobaltic-cobaltous oxide, by CoCl
2: MgSO
4: NbC
2o
4mol ratio be 0.98:0.01:0.01, preparation 3.3mol/L mixing material; The NaClO solution of the LiOH solution of mixing material and 3mol/L, 2mol/L is added in reactor to stirring reaction under 80 ℃, pH=7.5 condition by certain flow rate stream; Then after filtration, pure water washing, obtain intermediate product, under 400 ℃ of conditions, calcine 20h and obtain (Co
0.98mg
0.01nb
0.01)
3o
4, record D
50=9.5 um, AD=1.24 g/cm
3.
embodiment 2
A preparation method for spherical cobaltic-cobaltous oxide, by CoSO
4: Al
2(SO
4)
3mol ratio be 0.95:0.025, preparation 1mol/L mixing salt solution; By the NH of mixed solution and 2mol/L
4oH solution, high purity oxygen gas add in reactor by certain flow rate, stirring reaction under 40 ℃, pH=10.8 condition; Then after filtration, pure water washing, obtain intermediate product, under 600 ℃ of conditions, calcine 10 h and obtain (Co
0.95al
0.05)
3o
4, record D
50=20.5 um, AD=1.43g/cm
3.
embodiment 3
A preparation method for spherical cobaltic-cobaltous oxide, by Co(NO
3)-
2: Mn(NO
3)
2: n-ZrO
2mol ratio be 0.96:0.02:0.02, preparation 2mol/L mixing material; The NaOH solution of mixing material and 6mol/L, compressed air are added in reactor to stirring reaction under 70 ℃, pH=8.0 condition by certain flow rate stream; Then pass through centrifugally, pure water washing obtains intermediate product, calcines 5h and obtain (Co under 800 ℃ of conditions
0.96mn
0.02zr
0.02)
3o
4, record D
50=6.7 um, AD=1.08 g/cm
3.
embodiment 4
A preparation method for spherical cobaltic-cobaltous oxide, by CoSO
4: MgCl
2: Al
2(SO
4-)
3:: n-TiO
2mol ratio be 0.93:0.02:0.01:0.03, preparation 1.5mol/L mixing material; By the KOH solution of mixing material and 3mol/L, the H of 4mol/L
2o
-2the aqueous solution adds in reactor by certain flow rate stream, stirring reaction under 60 ℃, pH=9.0 condition; Then through centrifugal, pure water washing, obtains intermediate product, calcines 18h and obtain (Co under 450 ℃ of conditions
0.93mg
0.02al
0.02ti
0.03)
3o
4.Identical with cobaltosic oxide structure through X-ray diffraction analysis structure, record D
50=16.8 um, AD=1.37 g/cm
3.Lithium cobaltate cathode material prepared by this cobaltosic oxide, under circulation in 80 weeks, capability retention can reach more than 98%.
embodiment 5
A preparation method for spherical cobaltic-cobaltous oxide, by Co(AC)
2: TiOSO
4: AlCl
3mol ratio be 0.95:0.03:0.02, preparation 0.8mol/L mixing salt solution; By the NaOH solution of mixed solution and 12mol/L, 1mol/L Na
2s
2o
8by certain flow rate stream, add in reactor, under 50 ℃, the certain mixing speed of pH=9.3, react; Then through centrifugal, pure water washing, obtains intermediate product, calcines 6h and obtain (Co under 500 ℃ of conditions
0.95ti
0.03al
0.02)
3o
4, record D
50=12.6 um, AD=1.28g/cm
3.
Claims (13)
1. a preparation method for spherical cobaltic-cobaltous oxide, is characterized in that comprising the following steps: (1) adopts the mixing material containing cobalt, M and L of pure water preparation 0.5 ~ 3.5mol/L; (2) above-mentioned mixing material, precipitation reagent and oxidant stream add in reactor, stir lower reaction and obtain synthetic product; (3) through Separation of Solid and Liquid, washing, calcine to obtain end product.
2. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, is characterized in that in described mixing material, metal group becomes Co
(1-a-b)m
al
b, wherein the scope of a is 0 ﹤ a≤0.05, the scope of b is 0≤b≤0.05.
3. according to the preparation method of spherical cobaltic-cobaltous oxide described in claim 1 or 2, it is characterized in that described M is a kind of or wherein several in Ni, Mn, Cr, Fe, Mg, Ca, Sr, Ti, Ba, Zr, Sm, Al, Y or Zn; L is a kind of or wherein several in V, Nb, Ta, B, Ti, Sm, Zr, Mo, Hf or W.
4. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1 and 2, it is characterized in that cobalt in described mixing material with a kind of in cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt acetate or cobaltous formate or wherein several forms exist.
5. according to the preparation method of the spherical cobaltic-cobaltous oxide described in claim 1 or 3, it is characterized in that M in described mixing material with a kind of in sulfate, subsulfate, chlorate, alkali formula chloride, nitrate, subnitrate, acetate or formates or wherein several forms exist.
6. according to the preparation method of the spherical cobaltic-cobaltous oxide described in claim 1 or 3, it is characterized in that L in described mixing material with a kind of in hydroxide, oxide, oxyhydroxide, sulfide, nitride, carbide, fluoride, carbonate, phosphate or oxalates or wherein several forms exist.
7. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, is characterized in that described precipitation reagent is a kind of in ammoniacal liquor, NaOH, potassium hydroxide, lithium hydroxide or several mixture wherein; Precipitation reagent concentration is 0.5 ~ 15 mol/L.
8. the preparation method of spherical cobaltic-cobaltous oxide according to claim 1, is characterized in that described oxidant is a kind of in oxygen, air, hydrogen peroxide, clorox, sodium perchlorate, sodium peroxydisulfate, ozone, chlorine, sodium peroxide or several mixture wherein.
9. according to the preparation method of the spherical cobaltic-cobaltous oxide described in claim 1 or 7, the mol ratio that it is characterized in that precipitation reagent and the total salt of metal is 1.5 ~ 2.5.
10. according to the preparation method of the spherical cobaltic-cobaltous oxide described in claim 1 or 8, the mol ratio that it is characterized in that oxidant and the total salt of metal is 0.2 ~ 4.
The preparation method of 11. spherical cobaltic-cobaltous oxides according to claim 1, is characterized in that in described step (2), reaction condition is 7 ~ 12 for controlling pH value scope, and range of reaction temperature is 40 ~ 90 ℃.
The preparation method of 12. spherical cobaltic-cobaltous oxides according to claim 1, is characterized in that in described step (3), calcining heat is 400 ~ 800 ℃; Calcination time is 2 ~ 20h.
The preparation method of 13. spherical cobaltic-cobaltous oxides according to claim 1, is characterized in that described end product spherical cobaltic-cobaltous oxide powder is (Co
(1-a-b)m
al
b)
3o
4(0 ﹤ a≤0.05,0≤b≤0.05), D
50=5 ~ 25 um, AD>=1.0g/cm
3.
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