CN101841024A - Method for preparing cathode material lithium vanadium phosphate of lithium ion battery by using fast sol-gel method - Google Patents
Method for preparing cathode material lithium vanadium phosphate of lithium ion battery by using fast sol-gel method Download PDFInfo
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Abstract
The invention discloses a method for preparing a cathode material lithium vanadium phosphate of a lithium ion battery by using a fast sol-gel method, which specifically comprises the following steps of: (1) adding vanadic oxide into the solution of a reducing acid, heating the mixed solution to 60 to 80 DEG C and stirring the mixed solution for 10 to 50 minutes at a constant temperature to obtain blue solution; (2) adding lithium salts into the blue solution, wherein a stoichiometric ratio of the lithium salts to the vanadic oxide is 3-3.2: 2.9-3.05: 0.95-1.05; (3) treating an obtained powder material in an inert atmosphere at 200 to 400 DEG C for 2 to 4 hours to obtain a precursor; and (4) mixing and grinding uniformly the obtained precursor and another carbon source and cooling the mixture to obtain the cathode material lithium vanadium phosphate of the lithium ion battery. The method has the advantages that: (1) a synthesis process is simplified, the cost is reduced and the method is applied to industrial production; (2) the baking time is greatly shortened, the granularity of the product is reduced and the synthesized material has a nano-size; and (3) the carbon source is mixed before baking, carbon granules also can prohibit the growth of material granules and the synthesized material granules are uniform and fine.
Description
Technical field
The present invention relates to a kind of method for preparing cathode material lithium vanadium phosphate of lithium ion battery, relate in particular to the method that a kind of fast sol gel method prepares cathode material lithium vanadium phosphate of lithium ion battery.
Background technology
The chemical power source technology can realize conversion between chemical energy and the electric energy, the technology that stores safely, effectively as a kind of, starts research boom in the world.Lithium ion battery is considered one of chemical power source of tool potentiality because of advantage such as it has that volume is little, in light weight, operating voltage is high, specific energy is big, has extended cycle life, memory-less effect, self discharge are little.At present, lithium ion battery is at electric motor car (EV), hybrid electric vehicle (HEV), electric bicycle (EB), its special advantages of performance on the part market in electric tool fields such as (PT).And positive electrode is as the factor that influences lithium ion battery performance most critical, about its development.
At present, the lithium cobaltate cathode material of shiploads of merchandiseization, and Ni-Co-Mn element lithia material commonly used etc., though its capacity density height, fail safe is relatively poor.As power battery material,, there is very big potential safety hazard because high current charge-discharge easily causes burning even blast.On the other hand, the cobalt resource scarcity costs an arm and a leg, and also has heavy metal pollution.Therefore, seek safety, power lithium-ion battery positive electrode that cost performance is high has been an important research project.Studies show that so far, the power lithium-ion battery positive electrode of safety have LiMn
2O
4, LiFePO
4, Li
3V
2(PO
4)
3Deng.Li wherein
3V
2(PO
4)
3Advantage is more obvious, finds that it has and LiCoO
2Same discharge platform and energy density, and thermal stability, fail safe are far superior to LiCoO
2, also be better than LiMn
2O
4And LiFePO
4With LiFePO
4Compare monoclinic Li
3V
2(PO
4)
3Compound also has higher Li
+Ionic diffusion coefficient, higher discharge voltage (3.6V, 4.1V and 4.6V), higher theoretical specific capacity (197mAh/g) and energy density (2330mWh/cm
3After the doping carbon).Therefore, Li
3V
2(PO
4)
3Be considered to one of most promising new type power anode material for lithium-ion batteries, have potential application prospect aspect the high-capacity dynamical lithium-ion battery research and development.
Usually, the phosphoric acid vanadium lithium material is by solid phase method, sol-gal process, and certain methods such as hydrothermal synthesis method are synthesized.Show that according to the study granule-morphology has tremendous influence to the phosphoric acid vanadium lithium material property, product even, fine particle has bigger specific area, can improve the performance of material.Traditional solid phase method require repeatedly grinding, greater than 900 ℃ sintering temperatures and the roasting time that surpasses 16h, the material granule that obtains is bigger, inhomogeneous, and is easy to generate impurity; Methods such as hydrothermal synthesis method and rheology phase synthesi are higher to synthetic equipment requirements again, are difficult to be applicable to industrial production; And these methods relatively, reduce the particle of material at the mixing of sol-gal process on can realization response thing molecular level, have reduced the temperature of product roasting again, also are convenient to operation simultaneously.But traditional sol-gal process needs the time of a couple of days to obtain presoma usually, causes the overlong time of producing product, is unfavorable for realizing industrialization.
Summary of the invention
The object of the present invention is to provide a kind of fast sol gel method to prepare the method for cathode material lithium vanadium phosphate of lithium ion battery, the synthetic phosphoric acid vanadium lithium material granule of this method is tiny, even, and impurity is few, and has reduced sintering temperature, shortened roasting time.And than general sol-gal process, this method has shortened generated time greatly, has simplified synthesis step, and the product particle that obtains is evenly distributed, and possesses the good electric chemical property.
The present invention is achieved like this, and it is characterized in that concrete steps are:
(1) vanadic oxide is joined in the solution of reductive acid, vanadic oxide is 1 with the amount ranges ratio of reductive acid: 2.8-3.5, be heated to 60-80 ℃, and constant temperature stirs 10-50min, obtains blue solution;
(2) stoichiometric proportion of adding and vanadic oxide is lithium salts, phosphate and the solubility carbon source of 3-3.2: 2.9-3.05: 0.95-1.05 in blue solution, and constant temperature stirs 2-4h, and drying obtains xerogel, obtains powder after the grinding;
(3) dusty material that obtains is handled 2-4h in inert atmosphere under 200-400 ℃, obtain presoma;
(4) with the presoma that obtains and another kind of carbon source mixed grinding evenly after, in 500-850 ℃ of following roasting 2-4h, cooling obtains cathode material lithium vanadium phosphate of lithium ion battery in inert atmosphere.
The preferred oxalic acid of described reductive acid, citric acid.
Advantage of the present invention is: (1) generated time was foreshortened within the 24h by required time a couple of days of common sol gel method, had simplified synthesis technique, had reduced cost, was applicable to suitability for industrialized production; (2) roasting time shortens greatly, and sintering temperature is adjustable between 500-850 ℃, has effectively suppressed the undue growth of material grains, has reduced the granularity of product, and synthetic material particle size is nano-scale; (3) mixed carbon source before sintering, carbon granule also can suppress the growth of material grains, and the synthetic material granule that obtains is even, tiny.
Description of drawings
The X-ray diffraction spectrogram (a is the standard value in the inorganic crystal data storehouse among the figure) of Fig. 1 embodiment of the invention 1-embodiment 4 preparing products.
The product stereoscan photograph of Fig. 2 embodiment of the invention 1 preparation.
The product first charge-discharge curve of Fig. 3 embodiment of the invention 2 preparations.
The product of Fig. 4 embodiment of the invention 3 preparation is in the 3.0-4.8V interval, the cycle performance curve of testing under the 0.1C multiplying power.
The product of Fig. 5 embodiment of the invention 4 preparation is in the 3.0-4.3V interval, the cycle performance curve of testing under the 5C multiplying power.
Embodiment
Embodiment 1
The 0.03mol vanadium pentoxide powder is dissolved in the saturated solution of 0.1mol citric acid; 60 ℃ are stirred 15min down; add the lithium acetate of 0.093mol, the diammonium hydrogen phosphate of 0.09mol and the glucose of 0.2g then; continue to stir 4h; after 100 ℃ of following dryings, the following 300 ℃ of predecomposition 4h of argon shield mix the 0.2g polyaniline then and grind 2h; in the following 750 ℃ of roasting 4h of argon shield, be finished product Li after the cooling again
3V
2(PO
4)
3/ C.Resulting product shows through X-ray diffraction analysis, sees shown in the b among Fig. 1, without any impurity, is pure phase Li
3V
2(PO
4)
3Fig. 2 is the sem photograph of product, and as seen from the figure, the product size that makes is at nanoscale, and size is about 500-600nm, and the surface has coated the layer of even nano carbon particle.
Embodiment 2
The 0.02mol vanadium pentoxide powder is dissolved in the solution that contains 0.06mol oxalic acid; 80 ℃ are stirred 20min down; add the lithium chloride of 0.06mol, the ammonium dihydrogen phosphate of 0.061mol and the glucose of 0.25g then and continue to stir 2h; after 100 ℃ of following dryings; the following 350 ℃ of predecomposition 3h of nitrogen protection; mix the acetylene black of 0.25g then and grind 1h, in the following 800 ℃ of roasting 3h of nitrogen protection, be finished product Li after the cooling again
3V
2(PO
4)
3/ C.Resulting product shows through X-ray diffraction analysis, sees among Fig. 1 without any impurity, to be pure phase Li shown in the c
3V
2(PO
4)
3The first charge-discharge curve of this phosphoric acid vanadium lithium positive electrode as shown in Figure 3, specific discharge capacity can reach 158mAh/g in the 3.0-4.8V interval, charging/discharging voltage platform unanimity shows that material has good invertibity.
Embodiment 3
The vanadium pentoxide powder of 0.05mol is dissolved in the solution that contains 0.15mol oxalic acid; 65 ℃ are stirred 30min down; add the lithium carbonate of 0.0765mol, the sodium phosphate of 0.145mol and the polyethylene glycol (molecular formula is 300) of 1g then; continue to stir 3h; after 100 ℃ of following dryings, argon hydrogen gaseous mixture is protected following 400 ℃ of predecomposition 2h, mixes Super P then and grinds 2h; protect following 850 ℃ of roasting 2h in argon hydrogen gaseous mixture again, be finished product Li after the cooling
3V
2(PO
4)
3/ C.Resulting product shows through X-ray diffraction analysis, sees shown in the d among Fig. 1, without any impurity, is pure phase Li
3V
2(PO
4)
3This phosphoric acid vanadium lithium positive electrode is in the 3.0-4.8V interval, under the 0.1C multiplying power charge-discharge test as shown in Figure 4, high discharge capacity can reach 173mAh/g, and after 50 circulations, capability retention can reach 95%.
Embodiment 4
The vanadium pentoxide powder of 0.007mol is molten
In the 0.02mol lemonIn the saturated solution of lemon acid; 75 ℃ are stirred 30min down; add the lithium acetate of 0.02135mol, the ammonium dihydrogen phosphate of 0.021mol and the starch of 0.2g then; continue to stir 3h; after 100 ℃ of following dryings, the following 300 ℃ of predecomposition 2h of argon shield, mixed carbon black grinds 2h then; in the following 650 ℃ of roasting 4h of argon shield, be finished product Li after the cooling again
3V
2(PO
4)
3/ C.Resulting product shows through X-ray diffraction analysis, sees shown in the e among Fig. 1, without any impurity, is pure phase Li
3V
2(PO
4)
3Fig. 5 be this material in the 3.0-4.3V interval, the cycle life figure under the 5C rate charge-discharge test.Material is under the big multiplying power of 5C, and capability retention can reach 95% after 60 circulations.
Claims (2)
1. a fast sol gel method prepares the method for cathode material lithium vanadium phosphate of lithium ion battery, it is characterized in that concrete steps are:
(1) vanadic oxide is joined in the solution of reductive acid, vanadic oxide is 1 with the amount ranges ratio of reductive acid: 2.8-3.5, be heated to 60-80 ℃, and constant temperature stirs 10-50min, obtains blue solution;
(2) stoichiometric proportion of adding and vanadic oxide is lithium salts, phosphate and the solubility carbon source of 3-3.2: 2.9-3.05: 0.95-1.05 in blue solution, and constant temperature stirs 2-4h, and drying obtains xerogel, obtains powder after the grinding;
(3) dusty material that obtains is handled 2-4h in inert atmosphere under 200-400 ℃, obtain presoma;
(4) with the presoma that obtains and another kind of carbon source mixed grinding evenly after, in 500-850 ℃ of following roasting 2-4h, cooling obtains cathode material lithium vanadium phosphate of lithium ion battery in inert atmosphere.
2. a kind of fast sol gel method according to claim 1 prepares the method for cathode material lithium vanadium phosphate of lithium ion battery, it is characterized in that the preferred oxalic acid of described reductive acid, citric acid.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290575A (en) * | 2011-07-21 | 2011-12-21 | 中国电子科技集团公司第十八研究所 | Lithium ion cell anode material and preparation method thereof |
| CN102664263A (en) * | 2012-05-24 | 2012-09-12 | 陕西科技大学 | Preparation method of lithium ion battery cathode material carbon-coated columnar lithium vanadium phosphate |
| CN103094566A (en) * | 2013-01-24 | 2013-05-08 | 天津大学 | Sol gel method for preparing carbon-coated lithium-vanadium-phosphate as lithium battery positive pole material |
| CN103427080A (en) * | 2013-08-20 | 2013-12-04 | 天津大学 | Sol-gel method for preparing zinc-ion-modified carbon-coated lithium vanadium phosphate used as anode material of lithium ion battery |
| CN106025226A (en) * | 2016-07-13 | 2016-10-12 | 中国科学技术大学 | Cathode material for sodium-ion battery, preparation method of cathode material and sodium-ion battery |
| CN106549143A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of application of vanadium phosphate cathode material of doping boron in lithium ion battery |
| CN106549145A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of application of vanadium phosphate cathode material of doping sulphur in lithium ion battery |
| CN106784735A (en) * | 2017-02-06 | 2017-05-31 | 安徽鹰龙工业设计有限公司 | A kind of lithium battery composite positive pole and preparation method thereof |
| CN107010938A (en) * | 2017-04-28 | 2017-08-04 | 郑州大学 | A kind of method for suppressing to grow up under magnesium aluminate spinel nano particle high-temperature |
| CN108002356A (en) * | 2017-11-28 | 2018-05-08 | 华中农业大学 | δ-VOPO4Ultrathin nanometer piece and its controllable method for preparing and application |
| CN108232193A (en) * | 2018-01-25 | 2018-06-29 | 大连博融新材料有限公司 | A kind of vanadium series lithium ion battery positive electrode, its sol-gel process for preparing and purposes |
| CN109599544A (en) * | 2018-12-03 | 2019-04-09 | 攀枝花学院 | Phosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN110504422A (en) * | 2019-07-29 | 2019-11-26 | 全球能源互联网研究院有限公司 | A kind of cell positive material and preparation method thereof |
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2010
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290575A (en) * | 2011-07-21 | 2011-12-21 | 中国电子科技集团公司第十八研究所 | Lithium ion cell anode material and preparation method thereof |
| CN102664263A (en) * | 2012-05-24 | 2012-09-12 | 陕西科技大学 | Preparation method of lithium ion battery cathode material carbon-coated columnar lithium vanadium phosphate |
| CN103094566A (en) * | 2013-01-24 | 2013-05-08 | 天津大学 | Sol gel method for preparing carbon-coated lithium-vanadium-phosphate as lithium battery positive pole material |
| CN103427080A (en) * | 2013-08-20 | 2013-12-04 | 天津大学 | Sol-gel method for preparing zinc-ion-modified carbon-coated lithium vanadium phosphate used as anode material of lithium ion battery |
| CN106549145A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of application of vanadium phosphate cathode material of doping sulphur in lithium ion battery |
| CN106549143A (en) * | 2015-09-16 | 2017-03-29 | 中国科学院大连化学物理研究所 | A kind of application of vanadium phosphate cathode material of doping boron in lithium ion battery |
| CN106025226A (en) * | 2016-07-13 | 2016-10-12 | 中国科学技术大学 | Cathode material for sodium-ion battery, preparation method of cathode material and sodium-ion battery |
| CN106784735A (en) * | 2017-02-06 | 2017-05-31 | 安徽鹰龙工业设计有限公司 | A kind of lithium battery composite positive pole and preparation method thereof |
| CN107010938A (en) * | 2017-04-28 | 2017-08-04 | 郑州大学 | A kind of method for suppressing to grow up under magnesium aluminate spinel nano particle high-temperature |
| CN108002356A (en) * | 2017-11-28 | 2018-05-08 | 华中农业大学 | δ-VOPO4Ultrathin nanometer piece and its controllable method for preparing and application |
| CN108232193A (en) * | 2018-01-25 | 2018-06-29 | 大连博融新材料有限公司 | A kind of vanadium series lithium ion battery positive electrode, its sol-gel process for preparing and purposes |
| CN108232193B (en) * | 2018-01-25 | 2020-10-23 | 大连博融新材料有限公司 | Vanadium lithium ion battery anode material, and sol-gel preparation method and application thereof |
| CN109599544A (en) * | 2018-12-03 | 2019-04-09 | 攀枝花学院 | Phosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN109599544B (en) * | 2018-12-03 | 2020-11-10 | 攀枝花学院 | Lithium vanadium phosphate/carbon composite cathode material and preparation method thereof |
| CN110504422A (en) * | 2019-07-29 | 2019-11-26 | 全球能源互联网研究院有限公司 | A kind of cell positive material and preparation method thereof |
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Application publication date: 20100922 |