CN105206829A - Preparation method of high-voltage lithium ion battery cathode material - Google Patents
Preparation method of high-voltage lithium ion battery cathode material Download PDFInfo
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- CN105206829A CN105206829A CN201510711403.1A CN201510711403A CN105206829A CN 105206829 A CN105206829 A CN 105206829A CN 201510711403 A CN201510711403 A CN 201510711403A CN 105206829 A CN105206829 A CN 105206829A
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- lithium
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- anode material
- ion batteries
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
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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
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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
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
A cathode material occupies a quite important position for a lithium ion battery. Since 1990, by virtue of the advantages such as stable electrical performance and simple preparation process, LiCoO2 occupies a leading position of lithium ion battery cathode material markets for a long time. For improving defects of LiCoO2, researchers and manufacturers mainly adopt a coating or doping method for modification of LiCoO2, the electrical performance of LiCoO2 is improved to a certain extent after modification, but because of limitation of the modification method, the electrical performance of the product is difficult to guarantee under a condition of mass production. The lithium ion battery cathode material having high cut-off voltage (also called high voltage) is synthesized, and at the same time, the porous chain-shaped lithium cobaltate LiCoO2 cathode material having good multiplying power performance and cycle performance has secondary particle length of 3-20 microns and the diameter of 0.2-3 microns.
Description
Technical field
The present invention relates to a kind of preparation method of high-tension anode material for lithium-ion batteries, especially a kind of preparation method of high high voltage lithium cobalt oxide anode.
Background technology
Lithium ion battery has the unique advantages such as specific energy is high, operating voltage is high, self-discharge rate is low, have extended cycle life, be widely applied on various mobile device and electronic product as power supply now, future also plays larger effect by electrical source of power field.For lithium ion battery, positive electrode accounts for very important status.Since nineteen ninety Sony bring into use LiCoO
2since cell positive material, LiCoO
2the advantages such as the electrical property stable by means of it and simple preparation technology, occupy anode material for lithium-ion batteries leading market status for a long time.But LiCoO in current use
2the subject matter existed is: (1) cobalt resource is poisonous and cost is high; (2) actual capacity only has the 50-60% of theoretical capacity; (3) under high voltage, cycle performance can worsen; (4) under high and low temperature, electrical property performance has much room for improvement; (5) unsuitable quick charge.At present, in order to improve LiCoO
2defect, researcher and production firm mainly use coated or doping mode to LiCoO
2carrying out modification, through modified, though the electrical property of LiCoO2 has improvement to a certain degree, but due to the restriction of modified method, being difficult to, when when producing for large quantities of times, ensure the electrical property of product.
Summary of the invention
The object of the invention is to synthesize the anode material for lithium-ion batteries that one has high cut-ff voltage (or claiming " high voltage "), has the porous chain cobalt acid lithium LiCoO of good high rate performance and cycle performance simultaneously
2positive electrode, its second particle length 3-20 μm, diameter is at 0.2-3 μm.
Preparation method of the present invention comprises the following steps:
(1) it is in the oxalic acid solution of 0.12-2.2M that the ammonium salt solution of to be the cobalt salt solution of 0.1-2M and ammonium ion concentration by concentration of metal ions be 0-0.05M slowly joins concentration simultaneously, stir with the speed of 500-2000rpm, after metallic solution and ammonium salt solution dropwise, carrying out Separation of Solid and Liquid, washing leaching cake after continuing to stir 1-2h is about 7 rear dryings to washing lotion pH, obtains having porous club shaped structure cobalt oxalate presoma;
(2) the chain lithium cobaltate cathode material of pore structure is obtained having after carrying out two-section calcining after being mixed with lithium source by the cobalt oxalate presoma that above-mentioned steps (1) is obtained under air conditions.
Described in above-mentioned (1), cobalt salt solution comprises acetate corresponding to metallic element, sulfate, nitrate or the chlorate aqueous solution; Described ammonium salt solution comprises the aqueous solution of ammoniacal liquor, ammonium sulfate, ammonium carbonate, carbonic hydroammonium, ammonium nitrate or ammonium chloride.
Above-mentioned (1) mesoxalic acid solution usage is that oxalic acid and theoretical metal precipitate the 1.1-1.8 of consumption doubly, and preferred 1.1-1.6 doubly.
In above-mentioned (1), the speed that adds of metallic solution and ammonium salt solution is that in 1-5 hour, continuous uniform adds, or a point 3-5 batch (-type) adds, or has added according to the speed change that germination situation is slowed down gradually.
Described in above-mentioned (2), the proportioning in presoma and lithium source is preferably the excessive 2%-10% of lithium, and lithium source substance is chosen as one or more mixtures in lithium carbonate, lithium hydroxide and lithium nitrate.
8-30h is calcined at pre-burning 2-10h and 750-900 DEG C at two-section calcining described in above-mentioned steps (2) is followed successively by 400-600 DEG C.
invention advantage:
Compared with prior art, the invention has the advantages that:
(1) lithium cobaltate cathode material prepared by the present invention not only capacity is high, and its specific capacity can reach more than 165mAh/g, and due to chain structure little in radial direction size, lithium ion transport is apart from short and show higher high rate performance, and 5C/0.1C is greater than 70%.(2) loose structure makes it have larger specific surface, thus is conducive to lithium ion deintercalation, further raising capacity and high rate performance.(3) select kind and the concentration of ammonium salt according to the kind of cobalt salt raw material and concentration, adjust the speed of the acid-base value of solution and reaction, nucleation and germination, obtain required granule-morphology.(4) the method and hydroxide co-precipitation ratio, do not bring the foreign ion such as sodium, potassium into, product purity is high, and chemical property is good.(5) the method requires low to synthesis device, and technique is simple, and production efficiency is high, and accessory substance is mainly pure acid, recoverable, is therefore applicable to large-scale production.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the cobalt oxalate presoma of preparation in the embodiment of the present invention 1
Fig. 2 is the scanning electron microscope (SEM) photograph of the cobalt acid lithium of preparation in the embodiment of the present invention 1
Fig. 3 is the high rate performance figure of the cobalt acid lithium of preparation in the embodiment of the present invention 1
Fig. 4 is the X-ray diffracting spectrum of the cobalt acid lithium of preparation in the embodiment of the present invention 2
Fig. 5 is the 0.1C first charge-discharge curve chart of the cobalt acid lithium of preparation in the embodiment of the present invention 3
Fig. 6 is the 1C cycle graph of the cobalt acid lithium of preparation in the embodiment of the present invention 4.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
embodiment 1:
(1) cobaltous sulfate (CoSO is taken
47H
2o) 84.345g water-soluble after obtain that volume is 1L, concentration of metal ions is the solution of 0.3M, the 1L ammonium sulfate of itself and 0.01M is joined in the 1L oxalic acid solution that concentration is 0.32M with the speed of 10mL/min, control stir speed (S.S.) 500rpm simultaneously, after metallic solution and ammonium sulfate dropwise, Separation of Solid and Liquid after continuation stirring 2h, spend deionized water solid to cleaning solution pH value about 7, and at 80 DEG C, after drying, obtain that there is club shaped structure cobalt oxalate presoma.
(2) to get in above-mentioned (1) after obtained presoma 100g mixes with 21.29g lithium carbonate, (lithium carbonate excessive 2%), roasting 5h at 500 DEG C, is then warming up to 850 DEG C of 15h that bake with agglomeration, then obtains lithium ion cell anode material lithium cobaltate through cooling.
Precursor of lithium ionic cell positive material in the present embodiment and the pattern of lithium cobaltate cathode material are as depicted in figs. 1 and 2, presoma is club shaped structure, positive electrode is chain structure, the length of this chain lithium cobaltate cathode material is 12-15 μm, diameter is 1-2 μm, with this material be positive pole, lithium sheet is made into button cell for negative pole, under 0.1C, 0.5C, 1C, 5C multiplying power, cycle charge discharge electrical testing is carried out in 2.7-4.5V interval; Discharge capacity is 168mAh/g, 0.5C to gained excellent electrochemical performance: 0.1C first, capacity under 1C, 5C multiplying power reaches 155mAh/g, 150mAh/g and 121mAh/g respectively, and the capability retention after 300 times that circulates under 1C is 85.5%.
embodiment 2:
(1) cobalt acetate (C is taken
4h
6o
4co4H
2o) 24.91g water-soluble after obtain that volume is 1L, concentration of metal ions is the solution of 0.1M, by the 1L ammonia spirit of itself and 0.005M by divide equally 5 times, at interval of 30 minutes one ways, it is in the 1L oxalic acid solution of 0.12M that interval joins concentration, control stir speed (S.S.) 1200rpm simultaneously, after solution dropwises, Separation of Solid and Liquid after continuation stirring 1h, stop washing to cleaning solution pH value about 7 time with deionized water cyclic washing solid, and at 80 DEG C, after drying, obtain that there is club shaped structure cobalt oxalate presoma.
(2) to get in above-mentioned (1) after obtained presoma 100g mixes with 24.89g lithium hydroxide, (lithium hydroxide excessive 5%), roasting 5h at 450 DEG C, is then warming up to 750 DEG C of 25h that bake with agglomeration, then obtains lithium ion cell anode material lithium cobaltate through cooling.
Scanning analysis shows, and this presoma is club shaped structure, positive electrode is porous club shaped structure, and second particle length is 10-16 μm, and diameter is 0.5-1 μm; Battery detecting is prepared, gained excellent electrochemical performance by method described in embodiment 1; Discharge capacity is 170mAh/g, 0.5C to 0.1C first, capacity under 1C, 5C multiplying power reaches 156mAh/g, 152mAh/g and 117mAh/g respectively; Within 200 weeks, 1C charge/discharge capacity conservation rate is 86.3%.
embodiment 3:
Take cobalt nitrate (Co (NO
3)
26H
2o) 145.53g water-soluble after obtain that volume is 1L, concentration of metal ions is the solution of 0.5M, the 1L ammonia spirit of itself and 0.015M is joined in the 1L oxalic acid solution that concentration is 0.6M with the speed of 15mL/min, add speed after 30 minutes and reduce to 15mL/min, then add speed after 30 minutes and reduce to 5mL/min until added; Control stir speed (S.S.) 1500rpm simultaneously, after solution dropwises, continue to stir Separation of Solid and Liquid after 2.5h, stop washing to cleaning solution pH value about 7 time with deionized water cyclic washing solid, and at 80 DEG C, after drying, obtain that there is club shaped structure cobalt oxalate presoma.
(2) to get in above-mentioned (1) after obtained presoma 100g mixes with 41.28g lithium hydroxide, (lithium nitrate excessive 6%), roasting 3h at 550 DEG C, is then warming up to 800 DEG C of 10h that bake with agglomeration, then obtains lithium ion cell anode material lithium cobaltate through cooling.
Scanning analysis shows, and this presoma is club shaped structure, positive electrode is chain structure, and second particle length is 10-19 μm, and diameter is 2-3 μm; Battery detecting is prepared, gained excellent electrochemical performance by method described in embodiment 1; Discharge capacity is 165mAh/g, 0.5C to 0.1C first, capacity under 1C, 5C multiplying power reaches 152mAh/g, 150mAh/g and 123mAh/g respectively; Within 100 weeks, 1C charge/discharge capacity conservation rate is 88.9%.
embodiment 4:
(1) cobalt chloride (CoCl is taken
26H
2o) 237.93g water-soluble after obtain that volume is 1L, concentration of metal ions is the solution of 1M, the 0.8L ammonium chloride solution of itself and 0.02M is joined in the 1.5L oxalic acid solution that concentration is 1.5M with the speed of 5mL/min, control stir speed (S.S.) 2000rpm simultaneously, after solution dropwises, Separation of Solid and Liquid after continuation stirring 3h, stop washing to cleaning solution pH value about 7 time with deionized water cyclic washing solid, and at 80 DEG C, after drying, obtain that there is club shaped structure cobalt oxalate presoma.
(2) to get in above-mentioned (1) after obtained presoma 100g mixes with 20.45g lithium nitrate, 12.44g lithium hydroxide, (lithium excessive 5%, lithium nitrate: lithium hydroxide=1:1), roasting 10h at 400 DEG C, then be warming up to 900 DEG C of 5h that bake with agglomeration, then obtain lithium ion cell anode material lithium cobaltate through cooling.
Scanning analysis shows, and this presoma is club shaped structure, positive electrode is chain structure, and second particle length is 8-12 μm, and diameter is 1-2 μm; Battery detecting is prepared, gained excellent electrochemical performance by method described in embodiment 1; Discharge capacity is 169mAh/g, 0.5C to 0.1C first, capacity under 1C, 5C multiplying power reaches 156mAh/g, 148mAh/g and 127mAh/g respectively; Under 25 DEG C of room temperatures, 100 weeks 1C charge/discharge capacity conservation rates are 92%.Under 55 DEG C of high temperature, 100 weeks 1C charge/discharge capacity conservation rates are 91%.
Claims (7)
1. a preparation method for high-tension anode material for lithium-ion batteries, is characterized in that described high-tension anode material for lithium-ion batteries is the chain cobalt acid lithium with pore structure, consists of LiCoO
2, its second particle length 3-20 μm, diameter at 0.2-3 μm, the preparation process of this positive electrode is:
(1) it is in the oxalic acid solution of 0.12-2.2M that the ammonium salt solution of to be the cobalt salt solution of 0.1-2M and ammonium ion concentration by concentration of metal ions be 0-0.05M slowly joins concentration simultaneously, stir with the speed of 500-2000rpm, after metallic solution and ammonium salt solution dropwise, carrying out Separation of Solid and Liquid, washing leaching cake after continuing to stir 1-3h is about 7 rear dryings to washing lotion pH, obtains having porous club shaped structure cobalt oxalate presoma;
(2) the chain lithium cobaltate cathode material of pore structure is obtained having after carrying out two-section calcining after being mixed with lithium source by the cobalt oxalate presoma that above-mentioned steps (1) is obtained under air conditions.
2. the preparation method of a kind of high-tension anode material for lithium-ion batteries according to claim 1, is characterized in that described in step (1), cobalt salt solution comprises the aqueous solution of acetate corresponding to metallic element, sulfate, nitrate or chlorate.
3. the preparation method of a kind of high-tension anode material for lithium-ion batteries according to claim 1, is characterized in that described in step (1), ammonium salt solution comprises the aqueous solution of ammoniacal liquor, ammonium sulfate, ammonium carbonate, carbonic hydroammonium, ammonium nitrate or ammonium chloride.
4. the preparation method of a kind of high-tension anode material for lithium-ion batteries according to claim 1, is characterized in that oxalic acid solution consumption described in step (1) is that oxalic acid and theoretical metal precipitate the 1.1-1.6 of consumption doubly.
5. the preparation method of a kind of high-tension anode material for lithium-ion batteries according to claim 1, the speed that adds that it is characterized in that metallic solution and ammonium salt solution in described step (1) is that in 1-5 hour, continuous uniform adds, or batch (-type) adds several times, or add according to the speed change that germination situation is slowed down gradually.
6. the preparation method of a kind of high-tension anode material for lithium-ion batteries according to claim 1, it is characterized in that the proportioning in presoma and lithium source described in step (2) is preferably the excessive 2%-10% of lithium, lithium source substance is chosen as one or more mixtures in lithium carbonate, lithium hydroxide and lithium nitrate.
7. the preparation method of a kind of high-tension anode material for lithium-ion batteries according to claim 1, is characterized in that the two-section calcining described in step (2) calcines 8-30h at pre-burning 2-10h and 700-900 DEG C at being followed successively by 400-600 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1893151A (en) * | 2005-07-01 | 2007-01-10 | 深圳市比克电池有限公司 | Method for preparing lithium composite metal oxide |
| CN102163713A (en) * | 2011-03-17 | 2011-08-24 | 广州市香港科大***研究院 | Method for preparing high-voltage spinel anode material of lithium-ion secondary battery |
| CN104779383A (en) * | 2015-04-07 | 2015-07-15 | 四川大学 | Preparation method of high-specific-energy cathode material of lithium ion battery |
-
2015
- 2015-10-28 CN CN201510711403.1A patent/CN105206829A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1893151A (en) * | 2005-07-01 | 2007-01-10 | 深圳市比克电池有限公司 | Method for preparing lithium composite metal oxide |
| CN102163713A (en) * | 2011-03-17 | 2011-08-24 | 广州市香港科大***研究院 | Method for preparing high-voltage spinel anode material of lithium-ion secondary battery |
| CN104779383A (en) * | 2015-04-07 | 2015-07-15 | 四川大学 | Preparation method of high-specific-energy cathode material of lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| 韦向红等: ""草酸盐共沉淀法合成LiNi0.8Co0.1Mn0.1O2及电化学性能"", 《化工新型材料》 * |
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Application publication date: 20151230 |