CN110078132A - A kind of method that intermittence cladding prepares doped cobaltic-cobaltous oxide - Google Patents
A kind of method that intermittence cladding prepares doped cobaltic-cobaltous oxide Download PDFInfo
- Publication number
- CN110078132A CN110078132A CN201910330321.0A CN201910330321A CN110078132A CN 110078132 A CN110078132 A CN 110078132A CN 201910330321 A CN201910330321 A CN 201910330321A CN 110078132 A CN110078132 A CN 110078132A
- Authority
- CN
- China
- Prior art keywords
- solution
- cobalt
- reaction
- reaction kettle
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 105
- 238000005253 cladding Methods 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 227
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 81
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 80
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 52
- 239000010941 cobalt Substances 0.000 claims abstract description 50
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 50
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 44
- 239000004411 aluminium Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 36
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010936 titanium Substances 0.000 claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- RMOSMMUWFCLGCL-UHFFFAOYSA-N [W].[Nb].[Ta] Chemical compound [W].[Nb].[Ta] RMOSMMUWFCLGCL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 268
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 78
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- 230000015572 biosynthetic process Effects 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 42
- 229910021529 ammonia Inorganic materials 0.000 claims description 39
- 239000000463 material Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 21
- -1 aluminium cobalt hydroxide Chemical compound 0.000 claims description 18
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 11
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 10
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 10
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- VYRXEHAAIGOAIM-UHFFFAOYSA-A C(C)O.[Cl-].[Ta+5].[W+4].[Nb+5].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound C(C)O.[Cl-].[Ta+5].[W+4].[Nb+5].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] VYRXEHAAIGOAIM-UHFFFAOYSA-A 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000010348 incorporation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 86
- 235000013495 cobalt Nutrition 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 239000012452 mother liquor Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229910052715 tantalum Inorganic materials 0.000 description 7
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- VRMDJIADUMIQFE-UHFFFAOYSA-L [Co](O)O.[Ti] Chemical compound [Co](O)O.[Ti] VRMDJIADUMIQFE-UHFFFAOYSA-L 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- IWRAVVYDORMLAM-UHFFFAOYSA-L C([O-])([O-])=O.[Co+2].[Al+3] Chemical compound C([O-])([O-])=O.[Co+2].[Al+3] IWRAVVYDORMLAM-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 4
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- GAYPVYLCOOFYAP-UHFFFAOYSA-N [Nb].[W] Chemical compound [Nb].[W] GAYPVYLCOOFYAP-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910000989 Alclad Inorganic materials 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DSYGQOJJTJAWKY-UHFFFAOYSA-I [Nb+5].C(C)O.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Nb+5].C(C)O.[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] DSYGQOJJTJAWKY-UHFFFAOYSA-I 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZHJHZVFYOKVTOT-UHFFFAOYSA-H ethanol hexachlorotungsten Chemical compound C(C)O.[W](Cl)(Cl)(Cl)(Cl)(Cl)Cl ZHJHZVFYOKVTOT-UHFFFAOYSA-H 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of methods that intermittent cladding prepares doped cobaltic-cobaltous oxide, this method passes through the extension with generated time, the cobalt liquor concentration gradient being added in reaction kettle increases or reduces, the solid-to-liquid ratio of slurry in reaction kettle is adjusted simultaneously, Moist chemical synthesis goes out fine and close cobalt hydroxide, during synthesizing cobalt hydroxide, by aluminium by way of repeatedly coating, in titanium or niobium tungsten tantalum incorporation cobalt hydroxide, then pass through calcining, by the aluminium of layered distribution inside cobalt hydroxide, titanium or niobium tungsten tantalum uniformly diffuse in crystal, it is prepared and mixes aluminium, titanium or the equally distributed doped cobaltic-cobaltous oxide product of niobium tungsten tantalum.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of big grain of modification for being used to prepare high voltage cobalt acid lithium
Degree mixes aluminium cobaltosic oxide preparation method.
Background technique
Cobalt acid lithium is lithium ion battery prepared by positive electrode with light-weight, capacity is big, specific energy is high, operating voltage
Height, electric discharge is steady, is suitble to the features such as heavy-current discharge, good cycle, long service life, is mainly used in 3C digital domain.
Cobalt acid lithium just develops towards the direction of high voltage, high-pressure solid, high circulation performance, wants to raw material cobaltosic oxide
Ask higher and higher.Co3O4It is a kind of functional material with special construction and performance, conventional Co3O4Market, which has faced, gradually withers
The status of contracting, big granularity adulterate Co3O4The market demand gradually highlight.How research, which prepares the big granularity of high-performance, is mixed the oxidation of aluminium four
Three cobalts have become hot spot.
Chinese invention patent CN201510881580.4 discloses " a kind of big partial size high-density spherical cobaltic-cobaltous oxide
Preparation method ", specific production method are to pass through segmentation in cobalt carbonate synthesis phase cobalt carbonate as made from multiple circulation crystallization
Formula thermal decomposition makes cobalt carbonate exploded in the low temperature predecomposition stage, forms micro channel, in the high temperature thermal decomposition stage, particle
Surface densification, so that big partial size high-density spherical cobaltic-cobaltous oxide be prepared.This patent is needed in cobalt carbonate synthesis phase
Multiple circulation crystallization, process is cumbersome, is unfavorable for industrialized production.Chinese invention patent CN201210401514.9, discloses " one
Kind prepares the method and device of big partial size spherical cobaltic-cobaltous oxide ", specifically surveyed when preparing the cobaltosic oxide of predetermined particle diameter
The granularity of discharge outlet cobaltosic oxide particle is tried, it, will discharging if its granularity is less than the predetermined production partial size of cobaltosic oxide
Suspension in mouthful is passed through in reaction unit that the reaction was continued again, until the cobaltosic oxide grain of the reaction unit discharge outlet
When degree is not less than predetermined production partial size, the suspension is passed into filter press, spherical cobaltic-cobaltous oxide is obtained by filtration.China
Patent of invention CN201711217367.9 discloses " preparation method that a kind of big uniform particle sizes mix aluminium cobaltosic oxide " and specifically wraps
Include following steps: Step 1: mixing the synthesis of aluminium cobalt carbonate；It is taken off Step 2: mixing the washing of aluminium cobalt carbonate and will mix aluminium cobalt carbonate slurry
Water, then with the ammonium hydrogen carbonate or sal volatile that concentration is 10~50g/L or dissolved with CO2Aqueous solution washing mix aluminium
Cobalt carbonate removes corresponding anion, while preventing the sediment of surfaces of aluminum from hydrolysis occurs and generating sheet precipitate, so as to cause
Surfaces of aluminum is unevenly distributed.
Summary of the invention
That the purpose of the present invention is to provide a kind of production processes is simple and easy to control, by making to cobalt hydroxide intermittence alclad
The standby method of the cobaltosic oxide of uniform doping a kind of out.
The present invention is to be achieved through the following technical solutions:
A kind of intermittent coating preparation method of doped cobaltic-cobaltous oxide, specifically includes the following steps:
Step (a) matches liquid
Using cobalt salt as raw material, preparing the cobalt liquor that cobalt concentration is 20 ~ 40g/L is solution A；Configuring cobalt concentration is 140 ~ 160g/L's
Cobalt liquor is B solution；C solution: compound concentration is the ammonia spirit of 180g/L, and addition 5 ~ 20ml mass is dense in every liter of ammonia spirit
Then the hydrazine hydrate solution that degree is 80% is mixed with the sodium hydroxide solution of 200 ~ 300g/L of concentration and was both obtained；Configure doped chemical
Solution is solution D；
Step (b), synthetic reaction
When cobalt hydroxide synthetic reaction starts, B solution is added in solution A, at the same time, by A, B solution are in mixing and C is molten
Liquid cocurrent is also added in reaction kettle, cobalt hydroxide synthesis is carried out under stiring, when slurry volume reaches certain autoclave body in reaction kettle
When product, accurate filter is opened, slurry in reaction kettle is squeezed into accurate filter with pump and is concentrated, underflow material returns anti-
It answers and continues to synthesize in kettle, the additional amount for controlling above-mentioned solution keeps reaction kettle liquid level to remain constant；
After reaction carries out a period of time, stop that A, B mixed solution are added into reaction kettle, while by solution D and C solution cocurrent
It is added in reaction kettle and carries out the cladding of aluminium；
After being once covered to complete, continues cobalt hydroxide synthesis and be doped member again after cobalt hydroxide synthesizes a period of time
The cladding of element then proceeds by cobalt hydroxide synthesis and is doped the cladding of element again, then after synthesizing a period of time
Cobalt hydroxide synthesis is carried out, divides Multi-layers distributing in cobalt hydroxide particle doped chemical；
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged, is filtered, washed, dries, obtained big
Granularity adulterates cobalt hydroxide product；
Step (d), calcining
The big granularity doping cobalt hydroxide that step (c) obtains is calcined, big granularity doped cobaltic-cobaltous oxide product is obtained.
When the present invention prepares big granularity doping cobalt hydroxide, in the step (a), solution D: to use aluminum sulfate, nitric acid
Any one in aluminium or alchlor is configured to the aluminum solutions of 30 ~ 40g/L of aluminium mass concentration or for titanium mass concentration 30-
The titanyl sulfate solution of 40g/L or niobium tungsten tantalum chloride ethanol solution for concentration 30-40g/L.
When the present invention prepares big granularity doping cobalt hydroxide, in the step (b), 2 bodies are added in the B solution of 3 parts by volume
In the solution A of product part, B solution is added in solution A with the flow of 300L/h, at the same time, by A, B solution in mixing with
The flow velocity and C solution cocurrent of 500L/h is also added in reaction kettle.
Time difference when the present invention prepares big granularity doping cobalt hydroxide, in the step (b), when cobalt hydroxide synthesizes
For 20h, 30h, 40h, every time during cladding the flow of control doped chemical solution be 230 ~ 240L/h, pH value in reaction 8.4 ~
8.8,75 ~ 80 DEG C of reaction temperature, 200 ~ 250 revs/min of stirring intensity.
In step (b) of the present invention, synthetic reaction, the adding manner of replacement A, B solution take the A, B solution of isometric part, will
B solution is added in solution A with the flow of 250L/h, at the same time, A, B solution is molten with the flow velocity of 500L/h and C in mixing
Liquid cocurrent is also added in reaction kettle, changes technological parameter, final to prepare small grain size doped cobaltic-cobaltous oxide product.
When the present invention prepares small grain size doped cobaltic-cobaltous oxide product, in the step (a), solution D: being original with aluminium salt
Material, the sulfuric acid that the aluminum solutions or titanium mass concentration that configuration 750L aluminum concentration is 19.73 ~ 26.30g/L are 19.73-26.30g/L
The niobium tungsten tantalum ethanol solution that oxygen titanium solution or niobium tungsten tantalum concentration are 19.73 ~ 26.30g/L.
When the present invention prepares small grain size doped cobaltic-cobaltous oxide product, in the step (b), when cobalt hydroxide synthesizes when
Between be respectively 10h, 20h, 30h, the flow that doped chemical solution is controlled during the cladding is 250L/h, and pH value in reaction is
8.8-9.0, reaction time 1h, reaction temperature are 70-75 DEG C, and stirring intensity is 300-320 revs/min.
When the present invention prepares big or small grain size doped cobaltic-cobaltous oxide product, in the step (a), the cobalt salt is sulfuric acid
Any one in cobalt, cobalt nitrate or cobalt chloride；
The digestion time is 1 ~ 2h, dry to use tray drying using 80 ~ 90 DEG C of deionized waters suction filtration cylinder filtering and washing
Machine, temperature are 120 ~ 150 DEG C；
In the step (d), using the calcining of boat furnace is pushed away, calcination temperature is 750 DEG C~800 DEG C, and calcination time is 6~8h.
In the step (b), reaction kettle liquid level is kept to remain constant by adjusting the mother liquor amount exhausted.
Granularity obtained big mixes aluminium, titanium or niobium tungsten tantalum cobaltosic oxide product by means of the present invention are as follows: mix aluminium, titanium,
Or niobium tungsten tantalum amount is 0.6 ~ 0.8% and is evenly distributed, laser particle size D10In 12 ~ 15 μm, D50In 17 ~ 19 μm, D9022 ~ 25 μm,
Zhen Shi Mi Du≤2.0g/cm3, 1.0 ~ 3.0m of specific surface area2/ g, pattern are spherical or spherical.
Small grain size obtained mixes aluminium, titanium or niobium tungsten tantalum cobaltosic oxide product by means of the present invention are as follows: mix aluminium, titanium,
Or niobium tungsten tantalum amount is 0.6 ~ 0.8% and is evenly distributed, laser particle size D10At 1 ~ 3 μm, D50At 3~5 μm, D90At 6 ~ 9 μm, vibration density
Du≤2.0g/cm3, 1.0 ~ 3.0m of specific surface area2/ g, pattern are spherical or spherical.
The beneficial effects of the present invention are:
1. due to Ksp[Co (OH)2】=1.6×10-15；Ksp[Al(OH)3】=1.9×10-33, aluminium is different from the settling velocity of cobalt,
It is difficult to be co-precipitated, Moist chemical synthesis of the present invention goes out fine and close cobalt hydroxide of the laser particle size at 18 ~ 20 μm, in cobalt hydroxide synthesis process
It is middle to carry out intermittent multiple aluminium cladding, divide Multi-layers distributing in hydroxide aluminium, titanium or niobium tungsten tantalum by way of repeatedly coating
In cobalt granule, then by calcining, the aluminium of layered distribution, titanium or niobium tungsten tantalum are gradually diffused in crystal, be prepared aluminium,
Titanium or the equally distributed big granularity of niobium tungsten tantalum mix aluminium, titanium or niobium tungsten tantalum cobaltosic oxide product can be prepared using this technique
It mixes aluminium, titanium or niobium tungsten tantalum amount out to be 0.6 ~ 0.8% and be evenly distributed, laser particle size D10At 12 ~ 15 μm, D50At 17 ~ 19 μm, D90
At 22 ~ 25 μm, Zhen Shi Mi Du≤2.0g/cm3, 1.0 ~ 3.0m of specific surface area2/ g, pattern are four spherical or spherical oxidations three
Cobalt product.
2. it is cobalt source that high concentration and the cobalt liquor of low concentration, which is respectively configured, in the present invention, prepares big granularity and mix aluminium, titanium or niobium tungsten
When tantalum cobaltosic oxide product, the B solution of high concentration is added in the solution A of low concentration and is mixed, in the same with this of side plus B solution
When be also added in reaction kettle while by A, B mixed solution with C solution cocurrent, reach synthesis the incipient stage using low concentration cobalt it is molten
Liquid, and with the increase of generated time, making the concentration of the cobalt liquor entered in kettle is in be incremented by state, so that reaching reduces synthesis
Incipient stage cobalt hydroxide nucleus generation quantity is reacted, the growth of cobalt hydroxide is conducive to, is conducive to prepare compact crystallization equal
Even big granularity cobalt hydroxide.
3. it is cobalt source that high concentration and the cobalt liquor of low concentration, which is respectively configured, in the present invention, prepares big granularity and mix aluminium, titanium or niobium tungsten
When tantalum cobaltosic oxide product, the solution A of low concentration is added in the B solution of high concentration and is mixed, in the same with this of side plus solution A
When be also added in reaction kettle while by A, B mixed solution with C solution cocurrent, by synthesis the incipient stage using high concentration cobalt it is molten
Liquid, and with the increase of generated time, the concentration of synthesis cobalt liquor is reduced, it is brilliant to increase synthetic reaction incipient stage cobalt hydroxide
Karyogenesis quantity is conducive to the growth for inhibiting cobalt hydroxide, is conducive to prepare the uniform small grain size cobalt hydroxide of compact crystallization.
4. the present invention after synthesizing a period of time, is continued by being concentrated synthetic slurry and returning to underflow material in reaction kettle
Synthesis, continues in kettle to add A, B, C solution remains unchanged liquid level in kettle, so as to adjust the solid-to-liquid ratio of synthetic slurry in kettle,
The effective volume of reaction kettle is increased, one-pot production capacity is increased, improves utilization rate of equipment and installations.
5., since cobalt hydroxide is contacted with air, cobalt hydroxide surface is caused to hold during miscellaneous cobalt hydroxide is wrapped in preparation
It is easily oxidized, is unfavorable for the growth of cobalt hydroxide, avoid giving birth to by way of reducing agent hydrazine hydrate is added in precipitant solution
At cobalt hydroxide be oxidized, ensure that the fine and close growth of cobalt hydroxide particle.
Detailed description of the invention
Fig. 1 is the SEM figure that embodiment 1 prepares product；
Fig. 2 is the SEM figure that embodiment 2 prepares product；
Fig. 3 is the SEM figure that embodiment 3 prepares product；
Fig. 4 is the SEM figure that embodiment 4 prepares product；
Fig. 5 is the SEM figure that embodiment 4 prepares product；
Fig. 6 is the SEM figure that embodiment 4 prepares product；
Fig. 7 is the SEM figure that embodiment 7 prepares product；
Fig. 8 is the SEM figure that embodiment 8 prepares product；
Fig. 9 is the SEM figure that embodiment 9 prepares product；
Figure 10 is the SEM figure that embodiment 10 prepares product；
Figure 11 is the SEM figure that embodiment 11 prepares product.
Specific embodiment
Invention is further described in detail combined with specific embodiments below；
Embodiment 1
A kind of intermittent cladding prepares the method that big granularity mixes aluminium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 20g/L cobalt nitrate solution；The B solution of preparation is 15m3Cobalt concentration is 160g/L
Cobalt nitrate solution；The C solution of preparation: taking concentration is the ammonia spirit of 180g/L, and addition 5ml mass is dense in every liter of ammonia spirit
Then the hydrazine hydrate solution that degree is 80% is mixed according to volume ratio 0.1:1 with the sodium hydroxide solution that concentration is 200g/L and was both obtained；
The solution D of configuration is the aluminum nitrate solution that aluminium mass concentration is 30g/L.
Step (b), synthetic reaction
Solution A is added with the flow of 300L/h in B solution, while plus B solution at the same time while by A, B mixed solution with
The flow velocity and C solution cocurrent of 500L/h is added in reaction kettle, cobalt hydroxide synthesis is carried out under 200 revs/min of stirring, when anti-
When answering that slurry volume reaches the 80% of reaction kettle volume in kettle, accurate filter is opened, reaction kettle slurry is squeezed into precision with pump
It is concentrated in filter, underflow material returns to be continued to synthesize in reaction kettle, keeps reaction kettle by adjusting the mother liquor amount exhausted
Liquid level in reaction kettle volume 80%.Strict control pH value in reaction is 8.4 in reaction process, and reaction temperature is 75 DEG C, stirring intensity
It is 200 revs/min, reaction time 50h.After cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h, stop into reaction kettle
A, B mixed solution is added.Solution D is added in reaction kettle with the flow of 237.5L/h and C solution cocurrent simultaneously, at 200 revs/min
The cladding of aluminium is carried out under the stirring of clock, strict control pH value in reaction is 8.4 during cladding, and reaction temperature is 75 DEG C, and stirring is strong
Degree is 200 revs/min, reaction time 80min.After aluminium is added in reaction kettle several times, continue the conjunction of cobalt hydroxide
At.
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged.After being aged 1h, synthetic product is used
Suction filtration cylinder filtration washing, for washing material using 80 DEG C of deionized water, the equipment of dried material is tray drier, dry
Temperature is 120 DEG C, obtains big granularity multilayer and mixes aluminium cobalt hydroxide product.
Step (d), calcining
Obtained big granularity multilayer is mixed aluminium cobalt hydroxide on pushing away boat furnace to calcine, calcination temperature is 750 DEG C, and calcination time is
8h.It obtains big granularity and mixes aluminium cobaltosic oxide product, physical and chemical indexes are shown in Table 1, and product microscopic appearance index is shown in Fig. 1.
The product section physical and chemical indexes that table 1. is prepared using method in embodiment 1
Embodiment 2
A kind of intermittent cladding prepares the method that big granularity mixes aluminium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 30g/L cobalt sulfate solution；The B solution of preparation is 15m3Cobalt concentration is 150g/L
Cobalt sulfate solution；The C solution of preparation: taking concentration is the ammonia spirit of 180g/L, adds 15ml mass in every liter of ammonia spirit
Then the hydrazine hydrate solution that concentration is 80% both obtained for the sodium hydroxide solution of 250g/L according to volume ratio 0.15:1 with concentration；Match
The solution D set is the aluminum sulfate solution that aluminium mass concentration is 35g/L.
Step (b), synthetic reaction
Solution A is added with the flow of 300L/h in B solution, while add B solution at the same time while by A, B mixed solution with 500L/h
Flow velocity and C solution cocurrent be added reaction kettle in, under 220 revs/min of stirring carry out cobalt hydroxide synthesis, when in reaction kettle
When slurry volume reaches the 80% of reaction kettle volume, accurate filter is opened, reaction kettle slurry is squeezed into accurate filter with pump
In be concentrated, underflow material returns to be continued to synthesize in reaction kettle, keeps reaction kettle liquid level to exist by adjusting the mother liquor amount that exhausts
The 80% of reaction kettle volume.Strict control pH value in reaction is 8.6 in reaction process, and reaction temperature is 78 DEG C, stirring intensity 220
Rev/min, reaction time 50h.After cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h, stop being added into reaction kettle
A, B mixed solution.Solution D is added in reaction kettle with the flow of 232.8L/h and C solution cocurrent simultaneously, at 220 revs/min
The cladding of aluminium is carried out under stirring, strict control pH value in reaction is 8.6 during cladding, and reaction temperature is 78 DEG C, and stirring intensity is
220 revs/min, reaction time 80min.After aluminium is added in reaction kettle several times, continue the synthesis of cobalt hydroxide.
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged.After being aged 1.5h, by synthetic product
With suction filtration cylinder filtration washing, for washing material using 85 DEG C of deionized water, the equipment of dried material is tray drier, is done
Dry temperature is 140 DEG C, obtains big granularity multilayer and mixes aluminium cobalt hydroxide product.
Step (d), calcining
Obtained big granularity multilayer is mixed aluminium cobalt hydroxide on pushing away boat furnace to calcine, calcination temperature is 780 DEG C, and calcination time is
7h.It obtains big granularity and mixes aluminium cobaltosic oxide product, physical and chemical indexes are shown in Table 2, and product microscopic appearance index is shown in Fig. 2.
The product section physical and chemical indexes that table 2. is prepared using method in embodiment 2
Embodiment 3
A kind of intermittent cladding prepares the method that big granularity mixes aluminium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 40g/L cobalt chloride solution；The B solution of preparation is 15m3Cobalt concentration is 140g/L
Cobalt chloride solution；The C solution of preparation: taking concentration is the ammonia spirit of 180g/L, adds 20ml mass in every liter of ammonia spirit
Then the hydrazine hydrate solution that concentration is 80% both obtained for the sodium hydroxide solution of 300g/L according to volume ratio 0.2:1 with concentration；Match
The solution D set is the aluminum trichloride solution that aluminium mass concentration is 40g/L.
Step (b), synthetic reaction
Solution A is added with the flow of 300L/h in B solution, while add B solution at the same time while will by A, B mixed solution with
The flow velocity and C solution cocurrent of 500L/h is added in reaction kettle, cobalt hydroxide synthesis is carried out under 250 revs/min of stirring, when anti-
When answering that slurry volume reaches the 85% of reaction kettle volume in kettle, accurate filter is opened, reaction kettle slurry is squeezed into precision with pump
It is concentrated in filter, underflow material returns to be continued to synthesize in reaction kettle, keeps reaction kettle by adjusting the mother liquor amount exhausted
Liquid level in reaction kettle volume 85%.Strict control pH value in reaction is 8.8 in reaction process, and reaction temperature is 80 DEG C, stirring intensity
For, 250 revs/min, reaction time 50h.After cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h, stop to reaction kettle
Middle addition A, B mixed solution.Solution D is added in reaction kettle with the flow of 231L/h and C solution cocurrent simultaneously, at 250 revs/min
The cladding of aluminium is carried out under the stirring of clock, strict control pH value in reaction is 8.8 during cladding, and reaction temperature is 80 DEG C, and stirring is strong
Degree is 250 revs/min, reaction time 80min.After aluminium is added in reaction kettle several times, continue the conjunction of cobalt hydroxide
At.
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged.After being aged 2h, synthetic product is used
Suction filtration cylinder filtration washing, for washing material using 90 DEG C of deionized water, the equipment of dried material is tray drier, dry
Temperature is 150 DEG C, obtains big granularity multilayer and mixes aluminium cobalt hydroxide product.
Step (d), calcining
Obtained big granularity multilayer is mixed aluminium cobalt hydroxide on pushing away boat furnace to calcine, calcination temperature is 800 DEG C, and calcination time is
6h.It obtains big granularity and mixes aluminium cobaltosic oxide product, physical and chemical indexes are shown in Table 3, and product microscopic appearance index is shown in Fig. 3.
The product section physical and chemical indexes that table 3. is prepared using method in embodiment 3
Embodiment 4
A kind of intermittent cladding prepares the method that big granularity mixes titanium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 20g/L cobalt nitrate solution, and the B solution of preparation is 15m3Cobalt concentration is 160g/L
Cobalt nitrate solution；The C solution of preparation is the mixed liquor of sodium hydroxide solution and ammonia spirit: where sodium hydroxide solution is dense
Degree is 200g/L, and ammonia spirit concentration is 180g/L, and the hydrazine hydrate that addition 5ml mass concentration is 80% in every liter of ammonia spirit is molten
Liquid, and the volume ratio of the ammonia spirit and sodium hydroxide solution in C solution containing hydrazine hydrate is 0.1:1；The solution D of configuration is titanium matter
Measure the titanyl sulfate solution that concentration is 30g/L.
Step (b), synthetic reaction
When cobalt hydroxide synthetic reaction starts, B solution is added in solution A with the flow of 300L/h, at the same time, A, B solution
It is added in reaction kettle in mixing with the flow velocity of 500L/h and C solution cocurrent, hydroxide is carried out under 200 revs/min of stirring
Cobalt synthesis, when slurry volume reaches the 80% of reaction kettle volume in reaction kettle, accurate filter is opened, with pump by reaction kettle
Slurry is squeezed into accurate filter and is concentrated, and underflow material returns to be continued to synthesize in reaction kettle, by adjusting the mother liquor amount exhausted
To keep reaction kettle liquid level the 80% of reaction kettle volume.Strict control pH value in reaction is 8.4 in reaction process, and reaction temperature is
75 DEG C, stirring intensity is 200 revs/min, reaction time 50h.After cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h,
Stop cobalt hydroxide synthesis.Solution D is added in reaction kettle with the flow of 237.5L/h and C solution cocurrent simultaneously, 200 turns/
The cladding of titanium is carried out under the stirring of minute, strict control pH value in reaction is 8.4 during cladding, and reaction temperature is 75 DEG C, stirring
Intensity is 200 revs/min, reaction time 80min.After titanium is added in reaction kettle several times, continue cobalt hydroxide
Synthesis.
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed.Start to be aged, after being aged 1h, synthetic product is used
Suction filtration cylinder filtration washing, for washing material using 80 DEG C of deionized water, the equipment of dried material is tray drier, dry
Temperature is 120 DEG C, obtains big granularity multilayer and mixes titanium cobalt hydroxide product.
Step (d), calcining
Obtained big granularity multilayer is mixed titanium cobalt hydroxide on pushing away boat furnace to calcine, calcination temperature is 750 DEG C, calcination time 8h
It obtains big granularity and mixes titanium cobaltosic oxide product, physical and chemical indexes are shown in Table 4, and product microscopic appearance index is shown in Fig. 4.
The product section physical and chemical indexes that table 4. is prepared using method in embodiment 4
Embodiment 5
A kind of intermittent cladding prepares the method that big granularity mixes titanium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 40g/L cobalt chloride solution；The B solution of preparation is 15m3Cobalt concentration is 140g/L
Cobalt chloride solution；The C solution of preparation is the mixed liquor of sodium hydroxide solution and ammonia spirit: where sodium hydroxide solution is dense
Degree is 300g/L, and ammonia spirit concentration is 180g/L, and the hydrazine hydrate that addition 20ml mass concentration is 80% in every liter of ammonia spirit is molten
Liquid, and the volume ratio of the ammonia spirit and sodium hydroxide solution in C solution containing hydrazine hydrate is 0.2:1；The solution D of configuration is titanium matter
Measure the titanyl sulfate solution that concentration is 40g/L.
Step (b), synthetic reaction
When cobalt hydroxide synthetic reaction starts, B solution is added in solution A with the flow of 300L/h, at the same time, A, B solution
It is added in reaction kettle in mixing with the flow velocity of 500L/h and C solution cocurrent, hydroxide is carried out under 250 revs/min of stirring
Cobalt synthesis, when slurry volume reaches the 85% of reaction kettle volume in reaction kettle, accurate filter is opened, with pump by reaction kettle
Slurry is squeezed into accurate filter and is concentrated, and underflow material returns to be continued to synthesize in reaction kettle, by adjusting the mother liquor amount exhausted
To keep reaction kettle liquid level the 85% of reaction kettle volume.Strict control pH value in reaction is 8.8 in reaction process, and reaction temperature is
80 DEG C, stirring intensity is 250 revs/min, reaction time 50h.After cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h,
Stop cobalt hydroxide synthesis.Solution D is added in reaction kettle with the flow of 231L/h and C solution cocurrent simultaneously, at 300 revs/min
The cladding of titanium is carried out under the stirring of clock, strict control pH value in reaction is 8.8 during cladding, and reaction temperature is 80 DEG C, and stirring is strong
Degree is 300 revs/min, reaction time 80min.After titanium solution is added in reaction kettle several times, continue cobalt hydroxide
Synthesis.
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed.Start to be aged, after being aged 2h, synthetic product is used
Using 90 DEG C of deionized water, the equipment of dried material is tray drier, dry for suction filtration cylinder filtration washing, washing material
Temperature is 150 DEG C, obtains big granularity multilayer and mixes titanium cobalt hydroxide product.
Step (d), calcining
Obtained big granularity multilayer is mixed titanium cobalt hydroxide on pushing away boat furnace to calcine, calcination temperature is 800 DEG C, calcination time 6h
It obtains big granularity and mixes titanium cobaltosic oxide product, physical and chemical indexes are shown in Table 5, and product microscopic appearance index is shown in Fig. 5.
The product section physical and chemical indexes that table 5. is prepared using method in embodiment 5
Embodiment 6
A kind of intermittent cladding prepares the method that big granularity mixes niobium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
Prepare 10m3The cobalt nitrate that cobalt concentration is 20g/L is solution A, prepares 15m3The cobalt nitrate solution that cobalt concentration is 160g/L is
B solution；Dose volume is C solution than the mixed liquor of sodium hydroxide solution and ammonia spirit for 0.1:1: where sodium hydroxide
Solution concentration is 200g/L, and ammonia spirit concentration is 180g/L, the water that addition 5mL mass concentration is 80% in every liter of ammonia spirit
Close hydrazine solution；The four niobium chloride ethanol solutions that compound concentration is 30g/L are solution D.
Step (b), synthetic reaction
When synthetic reaction starts, B solution is added in solution A with the flow velocity of 300L/h, at the same time, A, B solution side are mixed
While being added in reaction kettle with the flow velocity of 500L/h and C solution cocurrent, cobalt hydroxide synthesis is carried out under stirring；Work as reaction kettle
When interior slurry volume reaches the 80% of reaction kettle volume, slurry is squeezed into accurate filter with pump and is concentrated, concentration slurry returns
It returns in reaction kettle and continues to synthesize, and it is always anti-for keeping slurry volume in reaction kettle by the mother liquor amount of adjusting discharge reaction kettle
Answer the 80% of autoclave body product.When cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h respectively, while by solution D with 237.5L/h's
The cladding that niobium is carried out under stirring is added in reaction kettle in flow velocity and C solution cocurrent, and the single coating reaction time is 80min,
Repeated multiple times synthesis and intermittent cladding process, divide Multi-layers distributing in cobalt hydroxide particle niobium.Wherein, entire synthetic reaction
In the process, control pH value in reaction is 8.4, and reaction temperature is 75 DEG C, stirring intensity 200r/min, and synthetic reaction total duration is
50h。
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged.After being aged 1h, synthetic product is adopted
With 80 DEG C of deionized water in suction filtration cylinder filtration washing, be dried at 120 DEG C after washing using tray drier, obtained
Big granularity multilayer mixes niobium cobalt hydroxide product.
Step (d), calcining
Above-mentioned big granularity multilayer is mixed into niobium cobalt hydroxide product using boat furnace is pushed away, 8h is calcined at 750 DEG C, obtains big granularity and mix niobium
Cobaltosic oxide product.Its physical and chemical indexes is shown in Table 6, and the microscopic appearance index of product is shown in Fig. 6.
Table 6. mixes the physical and chemical indexes of niobium cobaltosic oxide product using the big granularity of method preparation in embodiment 6
Embodiment 7
A kind of intermittent cladding prepares the method that big granularity mixes tungsten cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
Prepare 10m3The cobaltous sulfate that cobalt concentration is 30g/L is solution A, prepares 15m3The cobalt sulfate solution that cobalt concentration is 150g/L is
B solution；Dose volume is C solution than the mixed liquor of sodium hydroxide solution and ammonia spirit for 0.15:1: where sodium hydroxide
Solution concentration is 250g/L, and ammonia spirit concentration is 180g/L, the water that addition 15mL mass concentration is 80% in every liter of ammonia spirit
Close hydrazine solution；The tungsten hexachloride ethanol solution that compound concentration is 35g/L is solution D.
Step (b), synthetic reaction
When synthetic reaction starts, B solution is added in solution A with the flow velocity of 300L/h, at the same time, A, B solution side are mixed
While being added in reaction kettle with the flow velocity of 500L/h and C solution cocurrent, cobalt hydroxide synthesis is carried out under stirring；Work as reaction kettle
When interior slurry volume reaches the 80% of reaction kettle volume, slurry is squeezed into accurate filter with pump and is concentrated, concentration slurry returns
It returns in reaction kettle and continues to synthesize, and it is always anti-for keeping slurry volume in reaction kettle by the mother liquor amount of adjusting discharge reaction kettle
Answer the 80% of autoclave body product.When cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h respectively, while by solution D with 232.8L/h's
The cladding that tungsten is carried out under stirring is added in reaction kettle in flow velocity and C solution cocurrent, and the single coating reaction time is 80min,
Repeated multiple times synthesis and intermittent cladding process, divide Multi-layers distributing in cobalt hydroxide particle in tungsten.Wherein, entire synthetic reaction
In the process, control pH value in reaction is 8.6, and reaction temperature is 78 DEG C, stirring intensity 220r/min, and synthetic reaction total duration is
50h。
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged.After being aged 1.5h, by synthetic product
Using 85 DEG C of deionized water in suction filtration cylinder filtration washing, be dried at 140 DEG C after washing using tray drier, obtained
Tungsten cobalt hydroxide product is mixed to big granularity multilayer.
Step (d), calcining
Above-mentioned big granularity multilayer is mixed into tungsten cobalt hydroxide product using boat furnace is pushed away, 7h is calcined at 780 DEG C, obtains big granularity and mix tungsten
Cobaltosic oxide product.Its physical and chemical indexes is shown in Table 7, and the microscopic appearance index of product is shown in Fig. 7.
Table 7. mixes the physical and chemical indexes of tungsten cobaltosic oxide product using the big granularity of method preparation in embodiment 7
Embodiment 8
A kind of intermittent cladding prepares the method that big granularity mixes tantalum cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
Prepare 10m3The cobalt chloride that cobalt concentration is 40g/L is solution A, prepares 15m3The cobalt chloride solution that cobalt concentration is 140g/L is
B solution；Dose volume is C solution than the mixed liquor of sodium hydroxide solution and ammonia spirit for 0.2:1: where sodium hydroxide
Solution concentration is 300g/L, and ammonia spirit concentration is 180g/L, the water that addition 20mL mass concentration is 80% in every liter of ammonia spirit
Close hydrazine solution；The tantalic chloride ethanol solution that compound concentration is 40g/L is solution D.
Step (b), synthetic reaction
When synthetic reaction starts, B solution is added in solution A with the flow velocity of 300L/h, at the same time, A, B solution side are mixed
While being added in reaction kettle with the flow velocity of 500L/h and C solution cocurrent, cobalt hydroxide synthesis is carried out under stirring；Work as reaction kettle
When interior slurry volume reaches the 85% of reaction kettle volume, slurry is squeezed into accurate filter with pump and is concentrated, concentration slurry returns
It returns in reaction kettle and continues to synthesize, and it is always anti-for keeping slurry volume in reaction kettle by the mother liquor amount of adjusting discharge reaction kettle
Answer the 85% of autoclave body product.When cobalt hydroxide synthetic reaction carries out 20h, 30h, 40h respectively, while by solution D with the stream of 231L/h
The cladding that tantalum is carried out under stirring is added in reaction kettle in speed and C solution cocurrent, and the single coating reaction time is 80min, instead
Multiple multi-stage synthesis and intermittent cladding process, divide Multi-layers distributing in cobalt hydroxide particle tantalum.Wherein, entire synthetic reaction mistake
Cheng Zhong, control pH value in reaction are 8.8, and reaction temperature is 80 DEG C, stirring intensity 250r/min, and synthetic reaction total duration is 50h.
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged.After being aged 2h, synthetic product is adopted
With 90 DEG C of deionized water in suction filtration cylinder filtration washing, be dried at 150 DEG C after washing using tray drier, obtained
Big granularity multilayer mixes tantalum cobalt hydroxide product.
Step (d), calcining
Above-mentioned big granularity multilayer is mixed into tantalum cobalt hydroxide product using boat furnace is pushed away, 6h is calcined at 800 DEG C, obtains big granularity and mix tantalum
Cobaltosic oxide product.Its physical and chemical indexes is shown in Table 8, and the microscopic appearance index of product is shown in Fig. 8.
Table 8. mixes the physical and chemical indexes of tantalum cobaltosic oxide product using the big granularity of method preparation in embodiment 8
Embodiment 9
A kind of method that intermittent cladding preparation small grain size mixes aluminium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 20g/L cobalt nitrate solution；The B solution of preparation is 10m3Cobalt concentration is 160g/L
Cobalt nitrate solution；The C solution of preparation is the mixed liquor of sodium hydroxide solution and ammonia spirit: where sodium hydroxide solution is dense
Degree is 200g/L, and ammonia spirit concentration is 180g/L, and the hydrazine hydrate that addition 10ml mass concentration is 80% in every liter of ammonia spirit is molten
Liquid, and the volume ratio of the ammonia spirit and sodium hydroxide solution in C solution containing hydrazine hydrate is 0.05:1；The solution D of configuration is
750L aluminum concentration is the aluminum nitrate solution of 19.73g/L.
Step (b), synthetic reaction
When cobalt hydroxide synthetic reaction starts, solution A is added in B solution with the flow of 250L/h, at the same time, A, B solution
It is added in reaction kettle in mixing with the flow velocity of 500L/h and C solution cocurrent, hydroxide is carried out under 300 revs/min of stirring
Cobalt synthesis, when slurry volume reaches the 75% of reaction kettle volume in reaction kettle, accurate filter is opened, with pump by reaction kettle
Slurry is squeezed into accurate filter and is concentrated, and underflow material returns to be continued to synthesize in reaction kettle, by adjusting the mother liquor amount exhausted
To keep reaction kettle liquid level the 75% of reaction kettle volume.Strict control pH value in reaction is 8.8 in reaction process, and reaction temperature is
70 DEG C, stirring intensity is 300 revs/min, reaction time 40h.
Mix aluminium.When cobalt hydroxide synthetic reaction carries out 10h, 20h, 30h, stop cobalt hydroxide synthesis, while by D, C solution
It is added in reaction kettle the cladding for carrying out aluminium with certain flow velocity, after cladding process, continues cobalt hydroxide synthesis.Every time
Strict control reaction pH is 8.8 during cladding, and reaction temperature is 70 DEG C, and stirring intensity is 300 revs/min, and solution D flow velocity is
250L/h, reaction time 1h.
Step (c) is aged, is filtered, washed and dries
After all reaction kettle is added in A, B solution, accurate filter is closed, starts to be aged.After being aged 1h, synthetic product is taken out
Filtering jar filtration washing, washing material is using 80 DEG C of deionized water, and the equipment of dried material is tray drier, dry temperature
Degree is 120 DEG C, obtains small grain size and mixes aluminium cobalt hydroxide product.
Step (d), calcining
Obtained small grain size is mixed aluminium cobalt hydroxide on pushing away boat furnace to calcine, calcination temperature is 750 DEG C, and calcination time 8h is obtained
Aluminium cobaltosic oxide product is mixed to small grain size, physical and chemical indexes are shown in Table 9, and the microscopic appearance index of product is shown in Fig. 9.
The product section physical and chemical indexes that table 9. is prepared using method in embodiment 9
Embodiment 10
A kind of method that intermittent cladding preparation small grain size mixes titanium cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 30g/L cobalt sulfate solution, and the B solution of preparation is 10m3Cobalt concentration is 150g/L
Cobalt sulfate solution.The C solution of preparation is the mixed liquor of sodium hydroxide solution and ammonia spirit, wherein sodium hydroxide solution is dense
Degree is 250g/L, and ammonia spirit concentration is 180g/L, and the hydrazine hydrate that addition 15ml mass concentration is 80% in every liter of ammonia spirit is molten
Liquid, and the volume ratio of the ammonia spirit and sodium hydroxide solution in C solution containing hydrazine hydrate is 0.08:1；The solution D of configuration is
750L titanium concentration is the titanyl sulfate solution of 23.01g/L.
Step (b), synthetic reaction
When cobalt hydroxide synthetic reaction starts, solution A is added in B solution with the flow of 250L/h, at the same time, A, B solution
It is added in reaction kettle in mixing with the flow velocity of 500L/h and C solution cocurrent, hydroxide is carried out under 310 revs/min of stirring
Cobalt synthesis, when slurry volume reaches the 78% of reaction kettle volume in reaction kettle, accurate filter is opened, with pump by reaction kettle
Slurry is squeezed into accurate filter and is concentrated, and underflow material returns to be continued to synthesize in reaction kettle, by adjusting the mother liquor amount exhausted
To keep reaction kettle liquid level the 78% of reaction kettle volume.Strict control pH value in reaction is 8.9 in reaction process, and reaction temperature is
72 DEG C, stirring intensity be 310 revs/min, reaction time 40h.
When cobalt hydroxide synthetic reaction carries out 10h, 20h, 30h, stop cobalt hydroxide synthesis, while by D, C solution with one
Fixed flow velocity is added in reaction kettle the cladding for carrying out titanium, after cladding process, continues cobalt hydroxide synthesis.Cladding every time
Strict control reaction pH is 8.9 in the process, and reaction temperature is 72 DEG C, and stirring intensity is 310 revs/min, and solution D flow velocity is
250L/h, reaction time 1h.
Step (c) is aged, is filtered, washed and dries
After all reaction kettle is added in A, B solution, accurate filter is closed, starts to be aged.After being aged 1.5h, synthetic product is used
Suction filtration cylinder filtration washing, for washing material using 85 DEG C of deionized water, the equipment of dried material is tray drier, dry
Temperature is 140 DEG C, obtains small grain size and mixes titanium cobalt hydroxide product.
Step (d), calcining
Obtained small grain size is mixed titanium cobalt hydroxide on pushing away boat furnace to calcine, calcination temperature is 780 DEG C, and calcination time 7h is obtained
Titanium cobaltosic oxide product is mixed to small grain size, physical and chemical indexes are shown in Table 10, and the microscopic appearance index of product is shown in Figure 10.
The product section physical and chemical indexes that table 10. is prepared using method in embodiment 10
Embodiment 11
A kind of method that intermittent cladding preparation small grain size mixes niobium tungsten tantalum cobaltosic oxide, specifically includes the following steps:
Step (a) matches liquid
The solution A of configuration is 10m3Cobalt concentration is 40g/L cobalt chloride solution；The B solution of preparation is 10m3Cobalt concentration is 140g/L
Cobalt chloride solution；The C solution of preparation is the mixed liquor of sodium hydroxide solution and ammonia spirit: where sodium hydroxide solution is dense
Degree is 300g/L, and ammonia spirit concentration is 180g/L, and the hydrazine hydrate that addition 20ml mass concentration is 80% in every liter of ammonia spirit is molten
Liquid, and the volume ratio of the ammonia spirit and sodium hydroxide solution in C solution containing hydrazine hydrate is 0.1:1；The solution D of configuration is 500L
Niobium tungsten tantalum concentration is the tri-chlorination niobium tungsten tantalum solution of 26.30g/L.
Step (b), synthetic reaction
When synthetic reaction starts, solution A is added in B solution with the flow of 250L/h, at the same time, A, B solution are in mixing
It is added in reaction kettle with the flow velocity of 500L/h and C solution cocurrent, cobalt hydroxide synthesis is carried out under 320 revs/min of stirring, when
When slurry volume reaches the 80% of reaction kettle volume in reaction kettle, accurate filter is opened, reaction kettle slurry is squeezed into essence with pump
It is concentrated in close filter, underflow material returns to be continued to synthesize in reaction kettle, keeps reacting by adjusting the mother liquor amount exhausted
Kettle liquid position in reaction kettle volume 80%.Strict control pH value in reaction is 9.0 in reaction process, and reaction temperature is 75 DEG C, and stirring is strong
Degree is 320 revs/min, reaction time 40h.
Mix niobium tungsten tantalum.When cobalt hydroxide synthetic reaction carries out 10h, 20h, 30h, stop cobalt hydroxide synthesis, while by D, C
Solution is added in reaction kettle the cladding for carrying out niobium tungsten tantalum with certain flow velocity, after cladding process, continues cobalt hydroxide
Synthesis.Strict control reaction pH is 9.0 during cladding every time, and reaction temperature is 75 DEG C, and stirring intensity is 320 revs/min, D
Solution flow velocity is 250L/h, reaction time 1h.
Step (c) is aged, is filtered, washed and dries
After all reaction kettle is added in A, B solution, accurate filter is closed, starts to be aged.After being aged 2h, synthetic product is taken out
Filtering jar filtration washing, washing material is using 90 DEG C of deionized water, and the equipment of dried material is tray drier, dry temperature
Degree is 150 DEG C, obtains small grain size and mixes niobium tungsten tantalum cobalt hydroxide product.
Step (d), calcining
Obtained small grain size is mixed niobium tungsten tantalum cobalt hydroxide to calcine on pushing away boat furnace, calcination temperature is 800 DEG C, and calcination time is
6h obtains small grain size and mixes niobium tungsten tantalum cobaltosic oxide product., physical and chemical indexes are shown in Table 11, and the microscopic appearance index of product is shown in figure
11。
The product section physical and chemical indexes of 11. embodiment 11 of table
。
Claims (10)
1. a kind of method that intermittence cladding prepares doped cobaltic-cobaltous oxide, it is characterised in that: specifically includes the following steps:
Step (a) matches liquid
Using cobalt salt as raw material, preparing the cobalt liquor that cobalt concentration is 20 ~ 40g/L is solution A；Configuring cobalt concentration is 140 ~ 160g/L's
Cobalt liquor is B solution；C solution: compound concentration is the ammonia spirit of 180g/L, and addition 5 ~ 20ml mass is dense in every liter of ammonia spirit
Then the hydrazine hydrate solution that degree is 80% is mixed by volume with the sodium hydroxide solution of 200 ~ 300g/L of concentration and was both obtained；Configuration is mixed
The solution of miscellaneous element is solution D；
Step (b), synthetic reaction
When cobalt hydroxide synthetic reaction starts, B solution is added in solution A, at the same time, by A, B solution are in mixing and C is molten
Liquid cocurrent is also added in reaction kettle, cobalt hydroxide synthesis is carried out under stiring, when slurry volume reaches certain autoclave body in reaction kettle
When product, accurate filter is opened, slurry in reaction kettle is squeezed into accurate filter with pump and is concentrated, underflow material returns anti-
It answers and continues to synthesize in kettle, the additional amount for controlling above-mentioned solution keeps reaction kettle liquid level to remain constant；
After reaction carries out a period of time, stop that A, B mixed solution are added into reaction kettle, while by solution D and C solution cocurrent
It is added in reaction kettle and carries out the cladding of aluminium；
After being once covered to complete, continues cobalt hydroxide synthesis and be doped member again after cobalt hydroxide synthesizes a period of time
The cladding of element then proceeds by cobalt hydroxide synthesis and is doped the cladding of element again, then after synthesizing a period of time
Cobalt hydroxide synthesis is carried out, divides Multi-layers distributing in cobalt hydroxide particle doped chemical；
Step (c) is aged, is filtered, washed and dries
After A, B solution are all added in reaction kettle, accurate filter is closed, starts to be aged, is filtered, washed, dries, obtained big
Granularity mixes aluminium cobalt hydroxide product；
Step (d), calcining
The big granularity doping cobalt hydroxide that step (c) obtains is calcined, big granularity doped cobaltic-cobaltous oxide product is obtained.
2. the method that a kind of intermittent cladding according to claim 1 prepares doped cobaltic-cobaltous oxide, it is characterised in that: institute
It states in step (a), solution D: to be configured to aluminium mass concentration 30 using any one in aluminum sulfate, aluminum nitrate or alchlor
The aluminum solutions of ~ 40g/L or for titanium mass concentration 30-40g/L titanyl sulfate solution or be concentration 30-40g/L niobium tungsten tantalum
Chloride ethanol solution.
3. the method that a kind of intermittent cladding according to claim 2 prepares doped cobaltic-cobaltous oxide, it is characterised in that: institute
It states in step (b), the B solution of 3 parts by volume is added in the solution A of 2 parts by volume, B solution is molten with the flow addition A of 300L/h
In liquid, at the same time, A, B solution are also added in reaction kettle in mixing with the flow velocity of 500L/h and C solution cocurrent.
4. the method that a kind of intermittent cladding according to claim 3 prepares doped cobaltic-cobaltous oxide, it is characterised in that: institute
It states in step (b), time when cobalt hydroxide synthesizes is respectively 20h, 30h, 40h, controls doped chemical during cladding every time
The flow of solution is 230 ~ 240L/h, pH value in reaction 8.4 ~ 8.8,75 ~ 80 DEG C of reaction temperature, 200 ~ 250 revs/min of stirring intensity
Clock.
5. the method that a kind of intermittent cladding according to claim 1 prepares doped cobaltic-cobaltous oxide, it is characterised in that: step
Suddenly (b), in synthetic reaction, the adding manner of replacement A, B solution take the A, B solution of isometric part, by B solution with 250L/h's
Flow is added in solution A, at the same time, A, B solution is also added with the flow velocity of 500L/h with C solution cocurrent in mixing and reacted
It is final to prepare small grain size doped cobaltic-cobaltous oxide product in kettle.
6. the method that a kind of intermittent cladding according to claim 5 prepares doped cobaltic-cobaltous oxide, it is characterised in that: institute
It states in step (a), solution D: using aluminium salt as raw material, aluminum solutions or titanium matter that configuration 750L aluminum concentration is 19.73 ~ 26.30g/L
Measure the titanyl sulfate solution that concentration is 19.73-26.30g/L or the niobium tungsten tantalum ethyl alcohol that niobium tungsten tantalum concentration is 19.73 ~ 26.30g/L
Solution.
7. the method that a kind of intermittent cladding according to claim 6 prepares doped cobaltic-cobaltous oxide, it is characterised in that: institute
It states in step (b), time when cobalt hydroxide synthesizes is respectively 10h, 20h, 30h, and doped chemical is controlled during the cladding
The flow of solution is 250L/h, pH value in reaction 8.8-9.0, reaction time 1h, and reaction temperature is 70-75 DEG C, stirring intensity
It is 300-320 revs/min.
8. according to claim 1, a kind of intermittence cladding described in 2,3,4,5,6 or 7 prepares the side of doped cobaltic-cobaltous oxide
Method, it is characterised in that: in the step (a), the cobalt salt is any one in cobaltous sulfate, cobalt nitrate or cobalt chloride.
9. a kind of intermittent coating preparation method of doped cobaltic-cobaltous oxide according to claim 8, it is characterised in that: institute
Stating digestion time is 1 ~ 2h, dry to use tray drier, temperature using 80 ~ 90 DEG C of deionized waters suction filtration cylinder filtering and washing
Degree is 120 ~ 150 DEG C.
10. the method that a kind of intermittent cladding according to claim 9 prepares doped cobaltic-cobaltous oxide, it is characterised in that:
In the step (d), using the calcining of boat furnace is pushed away, calcination temperature is 750 DEG C~800 DEG C, and calcination time is 6~8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910330321.0A CN110078132A (en) | 2019-04-23 | 2019-04-23 | A kind of method that intermittence cladding prepares doped cobaltic-cobaltous oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910330321.0A CN110078132A (en) | 2019-04-23 | 2019-04-23 | A kind of method that intermittence cladding prepares doped cobaltic-cobaltous oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110078132A true CN110078132A (en) | 2019-08-02 |
Family
ID=67416327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910330321.0A Pending CN110078132A (en) | 2019-04-23 | 2019-04-23 | A kind of method that intermittence cladding prepares doped cobaltic-cobaltous oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078132A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825125A (en) * | 2020-09-16 | 2020-10-27 | 金驰能源材料有限公司 | Doped basic cobalt carbonate/cobalt carbonate composite precursor and preparation method and application thereof |
| CN112993243A (en) * | 2019-12-17 | 2021-06-18 | 格林美（江苏）钴业股份有限公司 | Preparation method of high-density aluminum-doped cobalt oxide |
| CN115676906A (en) * | 2022-10-26 | 2023-02-03 | 荆门市格林美新材料有限公司 | Bimetal alternately-doped cobaltosic oxide and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682271A (en) * | 2013-12-04 | 2014-03-26 | 天津巴莫科技股份有限公司 | Preparation method for multilayer shell-core structural lithium ion battery |
| CN105271441A (en) * | 2015-09-30 | 2016-01-27 | 兰州金川新材料科技股份有限公司 | Preparation method of battery-grade large-grained cobaltosic oxide |
| WO2017164963A9 (en) * | 2016-01-07 | 2017-11-23 | William Marsh Rice University | Facile preparation of carbon nanotube hybrid materials by catalyst solutions |
| CN108298596A (en) * | 2018-04-03 | 2018-07-20 | 兰州金川新材料科技股份有限公司 | A kind of preparation method of big granularity doped cobaltic-cobaltous oxide |
| CN108807880A (en) * | 2018-05-21 | 2018-11-13 | 兰州金川新材料科技股份有限公司 | A kind of gradient mixes the preparation method of niobium tungsten tantalum cobaltosic oxide |
-
2019
- 2019-04-23 CN CN201910330321.0A patent/CN110078132A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682271A (en) * | 2013-12-04 | 2014-03-26 | 天津巴莫科技股份有限公司 | Preparation method for multilayer shell-core structural lithium ion battery |
| CN105271441A (en) * | 2015-09-30 | 2016-01-27 | 兰州金川新材料科技股份有限公司 | Preparation method of battery-grade large-grained cobaltosic oxide |
| WO2017164963A9 (en) * | 2016-01-07 | 2017-11-23 | William Marsh Rice University | Facile preparation of carbon nanotube hybrid materials by catalyst solutions |
| CN108298596A (en) * | 2018-04-03 | 2018-07-20 | 兰州金川新材料科技股份有限公司 | A kind of preparation method of big granularity doped cobaltic-cobaltous oxide |
| CN108807880A (en) * | 2018-05-21 | 2018-11-13 | 兰州金川新材料科技股份有限公司 | A kind of gradient mixes the preparation method of niobium tungsten tantalum cobaltosic oxide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112993243A (en) * | 2019-12-17 | 2021-06-18 | 格林美（江苏）钴业股份有限公司 | Preparation method of high-density aluminum-doped cobalt oxide |
| JP2023507209A (en) * | 2019-12-17 | 2023-02-21 | 格林美（江蘇）鈷業股▲ふん▼有限公司 | Method for preparing high-density aluminum-doped cobalt oxide |
| JP7369298B2 (en) | 2019-12-17 | 2023-10-25 | 格林美（江蘇）鈷業股▲ふん▼有限公司 | Preparation method of high-density aluminum-doped cobalt oxide |
| US12006228B2 (en) | 2019-12-17 | 2024-06-11 | Gem (jiangsu) Cobalt Industry Co., Ltd. | Preparation method for high density aluminum doped cobalt oxide |
| CN111825125A (en) * | 2020-09-16 | 2020-10-27 | 金驰能源材料有限公司 | Doped basic cobalt carbonate/cobalt carbonate composite precursor and preparation method and application thereof |
| CN115676906A (en) * | 2022-10-26 | 2023-02-03 | 荆门市格林美新材料有限公司 | Bimetal alternately-doped cobaltosic oxide and preparation method and application thereof |
| CN115676906B (en) * | 2022-10-26 | 2024-04-16 | 荆门市格林美新材料有限公司 | Double-metal alternate doped cobaltosic oxide and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110078132A (en) | A kind of method that intermittence cladding prepares doped cobaltic-cobaltous oxide | |
| CN109311698B (en) | Ternary precursor material and preparation method thereof | |
| CN110217832A (en) | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide | |
| CN108598441B (en) | Different-granularity narrow-distribution ternary precursor and preparation method thereof | |
| CN110002513A (en) | A kind of preparation method of cobaltosic oxide | |
| JPH0222011B2 (en) | ||
| CN105271441A (en) | Preparation method of battery-grade large-grained cobaltosic oxide | |
| CN112357973A (en) | Preparation method of positive electrode material precursor and prepared positive electrode material precursor | |
| CN104828869B (en) | A kind of sodium manganese oxide micropowder and preparation method thereof | |
| CN110002514A (en) | A kind of preparation method of rare earth doped element cobaltosic oxide | |
| TW200808436A (en) | Device and process for the preparation of compounds by precipitation | |
| CN108298596A (en) | A kind of preparation method of big granularity doped cobaltic-cobaltous oxide | |
| CN108910932B (en) | Method for preparing narrow-distribution superfine yttrium oxide by sodium carbonate precipitation | |
| CN108807881A (en) | A kind of body mutually mixes the preparation method of aluminium cobaltosic oxide | |
| CN114057239B (en) | Preparation method of alkaline-water-washed high-nickel ternary precursor | |
| CN110611098B (en) | High-radiation and high-tap-density nickel-cobalt lithium aluminate precursor and preparation method thereof | |
| CN110071275A (en) | A kind of preparation method coating metal cobaltosic oxide | |
| CN108946824A (en) | A kind of preparation method of big granularity cobaltosic oxide | |
| CN105742568B (en) | A kind of nickel cobalt aluminum oxide and preparation method thereof | |
| CN108682849A (en) | A kind of preparation method for mixing aluminium cobalt acid lithium | |
| CN108455686A (en) | A kind of preparation method for mixing niobium tungsten tantalum cobaltosic oxide | |
| CN105293567B (en) | Flaky porous nanometer zinc oxide and preparation method thereof | |
| CN110092421A (en) | A kind of production method of the spherical basic cobaltous carbonate of size tunable | |
| CN104549527B (en) | A kind of preparation method of alumina support | |
| CN108483512A (en) | A kind of preparation method of big granularity cobaltosic oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190802 |
|
| RJ01 | Rejection of invention patent application after publication |