CN102842712A - Preparation method of cladded lithium cobalt oxide anode material - Google Patents
Preparation method of cladded lithium cobalt oxide anode material Download PDFInfo
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- CN102842712A CN102842712A CN2012103654817A CN201210365481A CN102842712A CN 102842712 A CN102842712 A CN 102842712A CN 2012103654817 A CN2012103654817 A CN 2012103654817A CN 201210365481 A CN201210365481 A CN 201210365481A CN 102842712 A CN102842712 A CN 102842712A
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- cobalt oxide
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- acid lithium
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a coated lithium cobalt oxide anode material. The preparation method comprises the following steps of: 1, preparing a primary lithium cobalt oxide material in a roll-type kiln by a high temperature solid state method according to the molar ratio, and then carrying out mechanical crushing and graded parameter regulation and control on the primary lithium cobalt oxide to obtain a primary graded lithium cobalt oxide material with concentrated particle size distribution; 2, putting the primary graded lithium cobalt oxide material into an autoclave digester containing clad materials and deionized water, continuously stirring to sufficiently mix under a certain pressure and temperature, and releasing pressure for material discharge; 3, drying slurry prepared in the step 2 at low temperature and screening; and 4, carrying out high-temperature solid phase sintering on the dried material, and carrying out mechanical crushing, classifying and cooling to obtain the finished product. The cladded lithium cobalt oxide anode material produced by using the preparation method disclosed by the invention has the characteristics of excellent electrochemical property, stable process and favorable safety and is suitable for industrial production.
Description
Technical field
The present invention relates to the lithium ion battery preparation field, particularly relate to a kind of preparation method of cladded type lithium cobaltate cathode material.
Background technology
Lithium cobaltate cathode material because of early-stage Study fully, the production technology comparative maturity becomes the anode material for lithium-ion batteries of present widespread commercialization, the cladded type lithium cobaltate cathode material becomes the object that many in recent years scholars and businessman research and develop because of the chemical property that can improve battery and security performance.
Coat layer of metal oxide type passivating film on cobalt acid lithium surface and can prevent that active material from directly contacting with electrolyte and reduce the dissolving of cobalt in electrolyte; Reduce cobalt acid lithium simultaneously and take off and adjoin the structural instability that phase transformation causes in Coulomb repulsion of oxygen layer and the removal lithium embedded process in the lattice that causes in the lithium process, can also improve capability retention and high rate performance simultaneously.
Cobalt acid lithium method for coating has solid phase method, sol-gel process, the precipitation method, ball-milling method and machinery-hot melt etc., and these method for coating covered effects are inhomogeneous and be not easy to carry out large-scale production.
Summary of the invention
To deficiency of the prior art, the purpose of this invention is to provide the preparation method of cladded type lithium cobaltate cathode material, prepared lithium cobaltate cathode material coats evenly, chemical property is excellent and be suitable for industrialization production.
For realizing above-mentioned purpose, technical scheme of the present invention is following:
A kind of preparation method of cladded type cobalt acid lithium material may further comprise the steps:
1) be 1.0～1.07 to carry out mechanical mixing with cobaltosic oxide and lithium carbonate by the mol ratio of Li/Co; Under 1000～1060 ℃, obtained cobalt acid lithium one defective material in 10～25 hours then, after mechanical disintegration, value parameter regulation and control obtain the cobalt acid lithium scalping material that particle size distribution is concentrated in roller-way stove calcining;
2) calculate according to cobaltosic oxide weight; Metal oxide with 0.1～0.4% and/or 0.1～0.4% metal hydroxides, 30～50% deionized water adds in the autoclave earlier, under room temperature has pressure, does not mix 0.5～1 hour; Again cobalt acid lithium scalping material is dropped in the autoclave; Blowing air also keep-ups pressure between 0.3～0.5Mpa, and continuous stirring is 5～8 hours under 110～150 ℃ of temperature, it is fully mixed make slurry;
3),, the material of drying is passed through the screening of 200 eye mesh screens 80～120 ℃ of following air blast oven dry with the prepared slurry cooling of second step;
4) material that screening is obtained is in that mechanical disintegration, classification can obtain finished product once more after 10～25 hours in roller-way stove calcining under 1000～1060 ℃ of temperature.
Preferably, the cobaltosic oxide in the said step 1) is a LITHIUM BATTERY.
Preferably; Said metal oxide is one or both in the oxide of Mg, Al, Cr, V, Ti, Y, Zr, Ru, Nb, Hf and Ta; Said hydroxide is the hydroxide of Mg, Al, Cr, V, Ti, Y, Zr, Ru, Nb, Hf or Ta, and the meso-position radius granularity of said metal oxide and metal hydroxides is less than 3 μ m.
The present invention boils the method that liquid phase combines through high temperature solid-state with pressing, and under certain temperature and pressure, adds the microscopic motion of fast particle, and material can fully mix and permeate, and prepares to coat evenly and the excellent lithium cobaltate cathode material of chemical property.
Description of drawings
Fig. 1 is the XRD figure of the cladded type cobalt acid lithium product of embodiment 1.
Embodiment
Below in conjunction with specific embodiment method of the present invention is elaborated.
Embodiment 1:
The first step with cobaltosic oxide and lithium carbonate in molar ratio Li/Co carry out behind the mechanical mixing in its saggar of packing into than the ratio that is 1.07; Push in the roller-way stove; Obtain cobalt acid lithium one defective material after 25 hours at 1000 ℃ temperature lower calcinations, after mechanical disintegration, value parameter regulation and control obtain the cobalt acid lithium scalping material that particle size distribution is concentrated;
Second step calculated according to cobaltosic oxide weight, will be 0.1%MgO, 0.3%Al (OH)
3Add earlier in the autoclave not have pressure under in room temperature with 50% deionized water and mixed 1 hour, with in the cobalt acid lithium classification material input autoclave, blowing air also keep-ups pressure at 0.4Mpa again, 110 ℃ of following continuous stirring 8 hours, it is fully mixed;
The 3rd step was cooled to room temperature with prepared slurry of second step, behind the release pressure material taking-up was positioned in the saggar, under 120 ℃, in air dry oven, dried, and crossed 200 eye mesh screens.
The 4th step pushed the saggar of loaded material in the 3rd step in the roller-way stove, 1030 ℃ of temperature lower calcinations 18 hours after mechanical disintegration and classification can obtain finished product.
The X ray diffracting spectrum of the product that Fig. 1 makes for present embodiment, its X ray diffracting spectrum is consistent with cobalt acid lithium.
Embodiment 2:
The first step with cobaltosic oxide and lithium carbonate in molar ratio Li/Co carry out behind the mechanical mixing in its saggar of packing into than the ratio that is 1.00; Push in the roller-way stove; Obtain cobalt acid lithium one defective material after 10 hours at 1060 ℃ temperature lower calcinations, after mechanical disintegration, value parameter regulation and control obtain the cobalt acid lithium scalping material that particle size distribution is concentrated;
Second step calculated according to cobaltosic oxide weight, will be 0.2%TiO
2, 0.1%RuO
2Add earlier in the autoclave not have pressure under in room temperature with 40% deionized water and mixed 0.5 hour, with in the cobalt acid lithium classification material input autoclave, blowing air also keep-ups pressure at 0.3Mpa again, 150 ℃ of following continuous stirring 5 hours, it is fully mixed;
The 3rd step was cooled to room temperature with prepared slurry of second step, behind the release pressure material taking-up was positioned in the saggar, under 80 ℃, in air dry oven, dried, and crossed 200 eye mesh screens.
The 4th step pushed the saggar of loaded material in the 3rd step in the roller-way stove, 1000 ℃ of temperature lower calcinations 25 hours after mechanical disintegration and classification can obtain finished product.
Embodiment 3:
The first step with cobaltosic oxide and lithium carbonate in molar ratio Li/Co carry out behind the mechanical mixing in its saggar of packing into than the ratio that is 1.03; Push in the roller-way stove; Obtain cobalt acid lithium one defective material after 15 hours at 1030 ℃ temperature lower calcinations, after mechanical disintegration, value parameter regulation and control obtain the cobalt acid lithium scalping material that particle size distribution is concentrated;
Second step calculated according to cobaltosic oxide weight, will be 0.4%Al
2O
3, 0.2%MgO and 30% deionized water add earlier in the autoclave in room temperature did not have pressure under mixing 0.5 hour; Again cobalt acid lithium classification material is dropped in the autoclave; Blowing air also keep-ups pressure at 0.5Mpa, 130 ℃ of following continuous stirring 7 hours, it is fully mixed;
The 3rd step was cooled to room temperature with prepared slurry of second step, behind the release pressure material taking-up was positioned in the saggar, under 100 ℃, in air dry oven, dried, and crossed 200 eye mesh screens.
The 4th step pushed the saggar of loaded material in the 3rd step in the roller-way stove, 1060 ℃ of temperature lower calcinations 10 hours after mechanical disintegration and classification can obtain finished product.
The chemical property of the cladded type cobalt acid lithium that above-mentioned three embodiment make is following:
Above experimental data shows; Adopt the 2032 type button cells test of the cladded type cobalt acid lithium material assembling of instance 1 production technology preparation; Its discharge cut-off voltage is 2.5V; The charging cut-ff voltage is 4.3V, and 0.1C discharge capacity first can reach 152mAh/g, and 400 all actual effect battery circulations reach 81% capability retention.Adopt the 2032 type button cells test of the cladded type cobalt acid lithium material assembling of instance 2 production technologies preparation; Its discharge cut-off voltage is 2.5V; The charging cut-ff voltage is 4.3V, and 0.1C discharge capacity first can reach 154mAh/g, and 400 all actual effect battery circulations reach 83% capability retention.Adopt the 2032 type button cells test of the cladded type cobalt acid lithium material assembling of instance 3 production technologies preparation; Its discharge cut-off voltage is 2.5V; The charging cut-ff voltage is 4.3V, and 0.1C discharge capacity first can reach 154mAh/g, and 400 all actual effect battery circulations reach 78% capability retention.
To sum up can see; This material is assembled into 2032 type button cells and tests, cut-ff voltage 2.5-4.3V, 0.1C first discharge capacity greater than 150mAh/g; 400 all actual effect battery circulations still can reach the capability retention more than 75%; Be very suitable for industrialization and produce in addition, and coat the layer of even metal oxide, also improved the security performance of battery to a certain extent on cobalt acid lithium material surface.
Claims (3)
1. the preparation method of cladded type cobalt acid lithium material is characterized in that may further comprise the steps:
1) be that 1.0～1.07 to carry out machinery mixed with cobaltosic oxide and lithium carbonate by the mol ratio of Li/Co; Under 1000～1060 ℃, obtained cobalt acid lithium one defective material in 10～25 hours then, after mechanical disintegration, value parameter regulation and control obtain the cobalt acid lithium scalping material that particle size distribution is concentrated in roller-way stove calcining;
2) in the weight of cobaltosic oxide; With percentage by weight is that the metal hydroxides of 0.1～0.4% metal oxide and/or 0.1～0.4%, 30～50% deionized water add in the autoclave; Under room temperature, normal pressure, stirred 0.5～1 hour, cobalt acid lithium scalping material is dropped in the autoclave again, blowing air also keep-ups pressure at 0.3～0.5MPa; 110～150 ℃ of following continuous stirring 5～8 hours, make slurry;
3) with step 2) cooling of the slurry that makes, cross the screening of 200 eye mesh screens 80～120 ℃ of following air blast oven dry backs;
4) material that screening is obtained is in that mechanical disintegration, classification can obtain finished product once more after 10～25 hours in the calcining of roller-way stove under 1000～1060 ℃.
2. method according to claim 1 is characterized in that: the cobaltosic oxide in the said step 1) is a LITHIUM BATTERY.
3. method according to claim 1; It is characterized in that: the metal oxide said step 2) is one or both in the oxide of Mg, Al, Cr, V, Ti, Y, Zr, Ru, Nb, Hf and Ta; Said hydroxide is the hydroxide of Mg, Al, Cr, V, Ti, Y, Zr, Ru, Nb, Hf or Ta, and the meso-position radius granularity of said metal oxide and metal hydroxides is less than 3 μ m.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103746114A (en) * | 2014-01-29 | 2014-04-23 | 厦门钨业股份有限公司 | Preparation method for lithium cobalt oxide anode material |
| CN103915619A (en) * | 2012-12-28 | 2014-07-09 | 北京当升材料科技股份有限公司 | Preparation method for composite lithium cobaltate material |
| CN105428625A (en) * | 2015-12-09 | 2016-03-23 | 山东齐星新材料科技有限公司 | Method for preparing alumina coated lithium cobalt oxide lithium ion battery material by aluminum salt solution aftertreatment |
| CN112820873A (en) * | 2020-12-31 | 2021-05-18 | 深圳市德方纳米科技股份有限公司 | Polymer-coated lithium battery positive electrode material and preparation method thereof |
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| CN102185138A (en) * | 2011-01-28 | 2011-09-14 | 厦门钨业股份有限公司 | Preparation method of composite lithium iron phosphate material |
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| CN102623690A (en) * | 2012-03-29 | 2012-08-01 | 天津巴莫科技股份有限公司 | Water washing and cladding method for high-nickel asymmetrical Li-Ni-Co-Mn-O compound material |
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- 2012-09-26 CN CN2012103654817A patent/CN102842712A/en active Pending
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| CN101150190A (en) * | 2007-10-30 | 2008-03-26 | 天津巴莫科技股份有限公司 | Anode material zirconium and phosphor adulterated lithium cobaltate of lithium ion secondary battery and its making method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103915619A (en) * | 2012-12-28 | 2014-07-09 | 北京当升材料科技股份有限公司 | Preparation method for composite lithium cobaltate material |
| CN103746114A (en) * | 2014-01-29 | 2014-04-23 | 厦门钨业股份有限公司 | Preparation method for lithium cobalt oxide anode material |
| CN103746114B (en) * | 2014-01-29 | 2016-11-16 | 厦门钨业股份有限公司 | A kind of preparation method of lithium cobaltate cathode material |
| CN105428625A (en) * | 2015-12-09 | 2016-03-23 | 山东齐星新材料科技有限公司 | Method for preparing alumina coated lithium cobalt oxide lithium ion battery material by aluminum salt solution aftertreatment |
| CN112820873A (en) * | 2020-12-31 | 2021-05-18 | 深圳市德方纳米科技股份有限公司 | Polymer-coated lithium battery positive electrode material and preparation method thereof |
| CN112820873B (en) * | 2020-12-31 | 2022-07-05 | 深圳市德方创域新能源科技有限公司 | Polymer-coated lithium battery positive electrode material and preparation method thereof |
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Application publication date: 20121226 |