CN103985855A - Preparation method of lithium battery cathode material solid solution micropowder - Google Patents
Preparation method of lithium battery cathode material solid solution micropowder Download PDFInfo
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- CN103985855A CN103985855A CN201310681154.7A CN201310681154A CN103985855A CN 103985855 A CN103985855 A CN 103985855A CN 201310681154 A CN201310681154 A CN 201310681154A CN 103985855 A CN103985855 A CN 103985855A
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- CN
- China
- Prior art keywords
- solid solution
- preparation
- lithium battery
- salt
- superfine powder
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a lithium battery cathode material solid solution micropowder. The method is characterized by comprising the following steps: (1) weighing and mixing Li salt, Mn salt, Ni salt and Co salt to obtain a metal salt mixture; (2) dissolving the metal salt mixture in deionized water to reach a concentration of 0.05-2 mol / L, and adding a thickening agent accounting for 2-35 wt.% of the metal salt mixture; (3) conducting spray drying on the product by using an airflow spray dryer to obtain a mixed powder; (4) pre-burning the powder at 400-600 DEG C for 3-6 h, and then heating to 800-1000 DEG C at a heating rate of 3-10 DEG C / min, and continuing burning for 10-25 h to obtain the solid solution powder. The product provided by the invention has excellent electrochemical properties, and the preparation process is simple and suitable for large-scale industrial production.
Description
Technical field
The invention belongs to new energy materials technical field, be specifically related to a kind of preparation method of anode material of lithium battery solid solution superfine powder.
Background technology
Along with people are to the growing of energy demand and deepening constantly society and economy sustainable development understanding of importance, more and more being subject to people's attention taking environmental protection and efficient high energy as the lithium ion battery of feature, all has higher requirement in the aspects such as the fail safe of the application such as big-and-middle-sized electric tool, energy-accumulating power station, electric motor car, intelligent grid to lithium ion battery, energy density, power density, cycle life, price, environmental friendliness.The specific capacity of lithium ion battery negative material is conventionally more than 300 mAh/g at present, and the specific capacity of positive electrode is hovered all the time in 150 mAh/g left and right.Therefore, positive electrode becomes the bottleneck that performance of lithium ion battery further improves.
H.Desilvestro in 2000 etc. have reported a kind of Olivine-type Cathode Material in Li-ion Batteries Li[Li
0.2mn
0.4cr
0.4] O
2its structure can be regarded L i as
2mnO
3and LiCrO
2the solid solution of composition, this material at room temperature discharge capacity can reach 260mAh/g, and under 55 ° of C, discharge capacity can reach 200mAh/g.In recent years, this with Li
2mnO
3and LiMO
2(M=Ni, Co, Cr, Fe, Al etc.) form the solid solution cathode material of composite construction, because it has height ratio capacity, high operating voltage, high-energy-density, the wider further investigation that charges and discharge voltage range, good thermal stability and the advantage such as cheap and attracted domestic and international experts and scholars, be considered to one of candidate's positive electrode of lithium ion battery of new generation.
At present, conventional method for preparing anode material of lithium-ion battery mainly contains: high temperature solid-state method, coprecipitation, sol-gel process, hydro thermal method etc.
High temperature solid-state method have equipment and process simple, be beneficial to the advantages such as suitability for industrialized production, but this method mixture homogeneity is limited; Coprecipitation can accurately be controlled the content of each component, makes to realize between dividing on the same group the even mixing of atom/molecule level; But standby powder may form agglomeration, thereby the characteristic of destruction powder, if therefore will prepare even, thin powder, just must strictly be controlled the preparation process of powder; The synthesis technique relative complex of sol-gal process and hydro thermal method, time-consuming power consumption cost is high, and is applicable to the research in laboratory more, amplifies to produce caused many difficulties for industrialization.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of preparation method of anode material of lithium battery solid solution superfine powder is provided.
For achieving the above object, the technical solution used in the present invention is as follows: a kind of preparation method of anode material of lithium battery solid solution superfine powder, is characterized in that: comprise the steps:
(1) by Li:Mn:Ni:Co=(4 ~ 12): (1 ~ 3): (1 ~ 3): the mol ratio of (0 ~ 2) takes Li salt, Mn salt, Ni salt, Co salt, obtains metal salt mixture after mixing;
(2) above-mentioned metal salt mixture is dissolved in deionized water, concentration is 0.05 ~ 2mol/L, then adds the thickener that accounts for metal salt mixture quality 2% ~ 35%;
(3) above-mentioned product utilization pneumatic spray drying device is sprayed and be dried, obtain mixed powder;
(4) by the first pre-burning 3 ~ 6 hours under 400 ~ 600 ° of C of above-mentioned powder, be then warmed up to 800 ~ 1000 ° of C, programming rate is 3 ~ 10 ° of C/min, continues calcining 10 ~ 25 hours, obtains solid solution superfine powder.
Slaine described in step (1) is nitrate, sulfate or acetate.
Thickener described in step (2) is polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA) or methylcellulose.
The charging rate of the spray dryer described in step (3) is 3 ~ 6mL/min, and inlet temperature is 220 ~ 250 ° of C, and outlet temperature is 130 ~ 150 ° of C.
Beneficial effect of the present invention: the present invention adopts spray drying process to prepare solid solution cathode material, prepared material is the superfine powder of hundreds of nanometer, the contact area that has improved electrode and electrolyte liquor has shortened lithium ion the evolving path, thereby improves power density and energy density.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
embodiment 1
In molar ratio for the ratio of 2:1:1 takes Li
2sO
4, MnSO
4and NiSO
4after being mixed, the slaine taking is dissolved in deionized water, be made into the solution that concentration is 0.3mol/L, add again the PVA thickener that accounts for metal salt mixture quality 5%, again soln using pneumatic spray drying device is sprayed dry, charging rate is 5mL/min, inlet temperature is 220 ° of C, outlet temperature is 140 ° of C, by the first pre-burning 4 hours under 500 ° of C of dried powder, be then warmed up to 900 ° of C, continue calcining 15 hours, programming rate is 5 ° of C/min, obtains solid solution Li[Li after cooling
0.2mn
0.4ni
0.4] O
2superfine powder.
embodiment 2
In molar ratio for the ratio of 4:1:1 takes Li
2sO
4, MnSO
4and NiSO
4after being mixed, the slaine taking is dissolved in deionized water, be made into the solution that concentration is 0.5mol/L, add again the PEG thickener that accounts for metal salt mixture quality 5%, again soln using pneumatic spray drying device is sprayed dry, charging rate is 3mL/min, inlet temperature is 220 ° of C, outlet temperature is 140 ° of C, by the first pre-burning 4 hours under 500 ° of C of dried powder, be then warmed up to 900 ° of C, continue calcining 15 hours, programming rate is 5 ° of C/min, obtains solid solution Li[Li after cooling
0.2mn
0.4ni
0.4] O
2superfine powder.
embodiment 3
In molar ratio for the ratio of 6:3:3:2 takes Li
2sO
4, MnSO
4, NiSO
4and CoSO
4after being mixed, the slaine taking is dissolved in deionized water, be made into the solution that concentration is 0.2mol/L, add again the PVP thickener that accounts for metal salt mixture quality 5%, again soln using pneumatic spray drying device is sprayed dry, charging rate is 5mL/min, inlet temperature is 220 ° of C, outlet temperature is 140 ° of C, by the first pre-burning 4 hours under 500 ° of C of dried powder, be then warmed up to 1000 ° of C, continue calcining 12 hours, programming rate is 5 ° of C/min, obtains solid solution Li[Li after cooling
0.2mn
0.4ni
0.4] O
2superfine powder.
Claims (4)
1. a preparation method for anode material of lithium battery solid solution superfine powder, is characterized in that: comprise the steps:
(1) by Li:Mn:Ni:Co=(4 ~ 12): (1 ~ 3): (1 ~ 3): the mol ratio of (0 ~ 2) takes Li salt, Mn salt, Ni salt, Co salt, obtains metal salt mixture after mixing;
(2) above-mentioned metal salt mixture is dissolved in deionized water, concentration is 0.05 ~ 2mol/L, then adds the thickener that accounts for metal salt mixture quality 2% ~ 35%;
(3) above-mentioned product utilization pneumatic spray drying device is sprayed and be dried, obtain mixed powder;
(4) by the first pre-burning 3 ~ 6 hours under 400 ~ 600 ° of C of above-mentioned powder, be then warmed up to 800 ~ 1000 ° of C, programming rate is 3 ~ 10 ° of C/min, continues calcining 10 ~ 25 hours, obtains solid solution superfine powder.
2. the preparation method of a kind of anode material of lithium battery solid solution superfine powder according to claim 1, is characterized in that: the slaine described in step (1) is nitrate, sulfate or acetate.
3. the preparation method of a kind of anode material of lithium battery solid solution superfine powder according to claim 1, is characterized in that: the thickener described in step (2) is polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA) or methylcellulose.
4. the preparation method of a kind of anode material of lithium battery solid solution superfine powder according to claim 1, it is characterized in that: the charging rate of the spray dryer described in step (3) is 3 ~ 6mL/min, inlet temperature is 220 ~ 250 ° of C, and outlet temperature is 130 ~ 150 ° of C.
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|---|---|---|---|
| CN201310681154.7A CN103985855A (en) | 2013-12-16 | 2013-12-16 | Preparation method of lithium battery cathode material solid solution micropowder |
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|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221225A (en) * | 1998-10-09 | 1999-06-30 | 清华大学 | Method for preparing lithium ion battery active material superfines with spray drying method |
| US20040091779A1 (en) * | 2002-11-01 | 2004-05-13 | The University Of Chicago | Layered cathode materials for lithium ion rechargeable batteries |
| JP2009004310A (en) * | 2007-06-25 | 2009-01-08 | Mitsubishi Chemicals Corp | Cathode active material for lithium secondary battery, cathode for lithium secondary battery using the same, and lithium secondary battery |
| US20120043500A1 (en) * | 2009-11-09 | 2012-02-23 | Qianxin Xiang | Polycrystalline cobalt-nicke-manganese ternary positive material, preparation method thereof and lithium ion secondary battery |
| CN102544456A (en) * | 2010-12-14 | 2012-07-04 | 苏州大学 | Cathode material of secondary battery and preparation method thereof as well as anode and secondary battery |
| CN102651474A (en) * | 2012-05-24 | 2012-08-29 | 四川科能锂电有限公司 | Preparation method of anode active material lithium iron phosphate of lithium battery |
-
2013
- 2013-12-16 CN CN201310681154.7A patent/CN103985855A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1221225A (en) * | 1998-10-09 | 1999-06-30 | 清华大学 | Method for preparing lithium ion battery active material superfines with spray drying method |
| US20040091779A1 (en) * | 2002-11-01 | 2004-05-13 | The University Of Chicago | Layered cathode materials for lithium ion rechargeable batteries |
| JP2009004310A (en) * | 2007-06-25 | 2009-01-08 | Mitsubishi Chemicals Corp | Cathode active material for lithium secondary battery, cathode for lithium secondary battery using the same, and lithium secondary battery |
| US20120043500A1 (en) * | 2009-11-09 | 2012-02-23 | Qianxin Xiang | Polycrystalline cobalt-nicke-manganese ternary positive material, preparation method thereof and lithium ion secondary battery |
| CN102544456A (en) * | 2010-12-14 | 2012-07-04 | 苏州大学 | Cathode material of secondary battery and preparation method thereof as well as anode and secondary battery |
| CN102651474A (en) * | 2012-05-24 | 2012-08-29 | 四川科能锂电有限公司 | Preparation method of anode active material lithium iron phosphate of lithium battery |
Non-Patent Citations (1)
| Title |
|---|
| CHAOCHAO FU等: "Gel-combustion synthesis of Li1.2Mn0.4Co0.4O2 composites with a high capacity and superior rate capability for lithium-ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
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Application publication date: 20140813 |
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