CN101262060B - A method for making anode material Li3V2(PO4)3 of lithium ion battery - Google Patents
A method for making anode material Li3V2(PO4)3 of lithium ion battery Download PDFInfo
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- CN101262060B CN101262060B CN200810031077XA CN200810031077A CN101262060B CN 101262060 B CN101262060 B CN 101262060B CN 200810031077X A CN200810031077X A CN 200810031077XA CN 200810031077 A CN200810031077 A CN 200810031077A CN 101262060 B CN101262060 B CN 101262060B
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- lithium
- vanadium
- phosphate
- source compound
- acid
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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
Abstract
The invention discloses a preparation method of lithium vanadium phosphate, a material for positive electrode of lithium ion battery. The preparation method of the invention comprises the steps that:high-valent vanadium compound, phosphorus compound and lithium compound are taken as raw materials and mixed according to molar ratio of contained vanadium, phosphorus and lithium is 2:3:3; the mixture is evenly mixed under room temperature and is added with a reducing agent, then mechanical activation is carried out; the molar ratio of the reducing agent and iron compound is controlled within 1:1-10:1; after 0.5-20 hours of activation and under normal temperature and pressure, the reducing agent is adopted to reduce high-valent vanadium compound so as to produce fine particles of amorphous Li3V2(PO4)3 which is then sent into non oxidizing atmosphere to be heated to 500-700 DEG C and calcined for 2-20 hours under constant temperature; then the crystalline state lithium vanadium phosphate powder is obtained. The preparation method of lithium vanadium phosphate adopts the low-temperature method to process the amorphous lithium vanadium phosphate so as to prepare the lithium vanadium phosphate with excellent performance, which greatly reduces energy consumption and cost. The lithium vanadium phosphate prepared by the preparation method of lithium vanadium phosphate has excellent charge/discharge performance.
Description
Technical field
The present invention relates to a kind of method for preparing cathode material lithium vanadium phosphate of lithium ion battery, particularly relate to the method that a kind of normal temperature reduction embedding lithium-Low Temperature Heat Treatment prepares cathode material lithium vanadium phosphate of lithium ion battery.
Background technology
Phosphoric acid vanadium lithium (Li
3V
2(PO
4)
3) be a kind of new type lithium ion battery positive electrode.It has higher discharge platform, and average discharge platform is about 4.0V; Higher charge/discharge capacity, in the voltage range of 3V～5V, theoretical capacity is 197mAh/g, reversible capacity is more than 170mAh/g; In the voltage range of 3V～4.5V, theoretical capacity is 133mAh/g; Good cycle performance; Good security performance, and cheap is considered to one of the most promising anode material for lithium-ion batteries in future, and to be expected to be used in the lithium ion battery be on the electric automobile of power, and its prospect is immeasurable.
Traditional preparation method mainly contains following several: high temperature solid-phase sintering method, carbothermic method, sol-gel process, hydro thermal method or the like.Yet all there are some intrinsic shortcomings in these methods, and as: synthesis temperature height, synthesis cycle is long, controlled condition is harsh, cost is high and the shortcomings such as charge-discharge performance difference of synthetic material, these are all limiting the extensive industrialization of phosphoric acid vanadium lithium.
Summary of the invention
It is low that technical problem to be solved by this invention provides a kind of synthesis temperature, and synthesis cycle is short, and condition control is easy, and synthetic method is simple, is easy to realize the method for preparing cathode material lithium vanadium phosphate of lithium ion battery of extensive industrialization.
In order to solve the problems of the technologies described above, the method for preparing cathode material lithium vanadium phosphate of lithium ion battery provided by the invention, with high price vanadium source compound, P source compound, Li source compound is a raw material, with the vanadium source compound, P source compound and Li source compound are pressed vanadium, phosphorus, the elemental lithium mol ratio is 2: 3: 3 a mixed, this mixture is at room temperature mixed, then add reducing agent, carry out mechanical activation then, soak time was controlled between 0.5～20 hour, the mol ratio of reducing agent and high price vanadium source compound is controlled between 1: 1～10: 1, under normal temperature and pressure conditions, incite somebody to action the reduction of high price vanadium and prepare the tiny unformed Li of particle with this reducing agent
3V
2(PO
4)
3, in non-oxidizing atmosphere, be heated to 500～700 ℃ then, and calcining at constant temperature 2～20 hours, make the phosphoric acid vanadium lithium powder of crystalline state.
Above-described described high price vanadium source compound is selected a kind of in vanadic oxide, vanadium dioxide, metavanadic acid ammonia, carbonic acid vanadium, the vanadium tetrachloride.Described P source compound is selected a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid, phosphorus pentoxide and the diphosphorus trioxide.Described Li source compound is selected a kind of in lithium carbonate, lithium formate, lithium hydroxide, lithium acetate, lithium fluoride, lithium iodide, lithia, lithium bromide and the lithium chloride.Described reducing agent is selected a kind of in ascorbic acid, ethanedioic acid, adipic acid, malonic acid, mandelic acid, malic acid, lactic acid, citric acid, formaldehyde, acetaldehyde, hutanal, isobutylaldehyde, tetraethyl ethylene glycol, isopropyl alcohol, the ethylene glycol.Described non-oxidizing gas is selected a kind of in argon gas, helium, neon, nitrogen, the hydrogen.
The phosphoric acid vanadium lithium particle that adopts said method to synthesize is tiny and particle size distribution is even, and electron conduction is significantly improved, and has the favorable charge-discharge performance; Normal temperature reduction embedding lithium-Low Temperature Heat Treatment provided by the invention prepares anode material for lithium-ion batteries Li
3V
2(PO
4)
3Method compare with prior preparation method, its advantage is in particular in following aspect:
1) is the vanadium source with high price vanadium source compound, greatly reduces synthesis condition and raw-material cost.
2) at normal temperatures and pressures, utilize reducing agent directly to incite somebody to action the unformed Li that the high price vanadium reduces and synthesizes the tiny stable in properties of particle
3V
2(PO
4)
3, solved trivalent vanadium ion oxidized problem easily.
3) adopt the unformed Li of Low Temperature Heat Treatment
3V
2(PO
4)
3And prepare the Li of function admirable
3V
2(PO
4)
3Greatly reduce the synthetic energy consumption of material, thereby reduced synthetic cost.
4) Li for preparing in this way
3V
2(PO
4)
3In the voltage range of normal temperature and pressure 3V～4.5V, specific discharge capacity is up to being under the 0.1C discharge-rate: 131mAhg
-1, reach theoretical capacity (133mAhg
-1) 98.5%, 50 circulation back capability retention more than 98%; Material has good charge-discharge performance.
In sum, the present invention is that a kind of synthesis temperature is low, and synthesis cycle is short, and condition control is easy, and synthetic method is simple, is easy to realize the method for preparing cathode material lithium vanadium phosphate of lithium ion battery of extensive industrialization.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of No. 3 samples among the embodiment 1;
Fig. 2 is the electron-microscope scanning figure of No. 3 samples among the embodiment 1;
Fig. 3 is the charging and discharging curve figure of No. 3 samples among the embodiment 1.
Embodiment
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment 1:
With vanadic oxide, lithium carbonate, ammonium dihydrogen phosphate and malic acid is raw material, 1: 1.5: 3 in molar ratio: 1 mixes, and mechanical activation 0.5 hour; Pack into then in the tube furnace, under argon gas atmosphere, temperature is respectively 500 ℃, 560 ℃, 650 ℃ and 700 ℃ of constant temperature 12 hours.The material of gained is a monoclinic form through X-ray diffraction analysis, is Li
3V
2(PO
4)
3Structure.Can obtain the particle diameter of product at 100～200nm by SEM.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, their discharge capacity first and the circulation 50 times after discharge capacity see Table 1
The experiment condition of table 1 embodiment 1 and result
Embodiment 2:
With vanadium dioxide, lithium formate, triammonium phosphate and mandelic acid is raw material, 2: 3: 3 in molar ratio: 3 mix, and mechanical activation 20 hours; Pack into then in the tube furnace, under hydrogen atmosphere, temperature respectively 650 ℃ of constant temperature 2h, 5h, 8h, 20 hours.The material of gained is a monoclinic form through X-ray diffraction analysis, is Li
3V
2(PO
4)
3Structure.Can obtain the particle diameter of product at 100～200nm by SEM.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, their discharge capacity first and the circulation 50 times after discharge capacity see Table
The experiment condition of table 2 embodiment 2 and result
Embodiment 3:
With metavanadic acid ammonia, lithia, diammonium hydrogen phosphate, ethanedioic acid is raw material, 2: 1.5: 3 in molar ratio: 4 mix, and mechanical activation 8 hours; Pack into then in the tube furnace, under nitrogen atmosphere, temperature was 550 ℃ of constant temperature 15 hours.The material of gained is a monoclinic form through X-ray diffraction analysis, is Li
3V
2(PO
4)
3Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first discharge capacity 131.5mAhg
-1, discharge capacity 130mAhg after 50 times circulates
-1
Embodiment 4:
With carbonic acid vanadium, lithium chloride, ammonium dihydrogen phosphate, lactic acid is raw material, 2: 3: 3 in molar ratio: 5 mix, and mechanical activation 10 hours; Pack into then in the tube furnace, under helium atmosphere, temperature was 650 ℃ of constant temperature 18 hours.The material of gained is a monoclinic form through X-ray diffraction analysis, is Li
3V
2(PO
4)
3Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first discharge capacity 130mAhg
-1, discharge capacity 129.5mAhg after 50 times circulates
-1
Embodiment 5:
With vanadium tetrachloride, lithium fluoride, phosphoric acid, acetaldehyde is raw material, 2: 3: 3 in molar ratio: 3 mix, and mechanical activation 15 hours; Pack into then in the tube furnace, under argon gas atmosphere, temperature was 650 ℃ of constant temperature 18 hours.The material of gained for for monoclinic form, is Li through X-ray diffraction analysis
3V
2(PO
4)
3Structure.Resulting product is assembled into button cell surveys its charging and discharging capacity and cycle performance, under the multiplying power of 0.1C, discharge and recharge, first discharge capacity 128mAhg
-1, discharge capacity 127.6mAhg after 50 times circulates
-1
In the foregoing description, P source compound can also be selected phosphorus pentoxide or diphosphorus trioxide.Li source compound can also be selected lithium hydroxide, lithium acetate, lithium iodide or lithium bromide.Reducing agent can also be selected a kind of in ascorbic acid, adipic acid, malonic acid, citric acid, formaldehyde, hutanal, isobutylaldehyde, tetraethyl ethylene glycol, isopropyl alcohol, the ethylene glycol.
Claims (6)
1. method for preparing cathode material lithium vanadium phosphate of lithium ion battery, it is characterized in that: with high price vanadium source compound, P source compound, Li source compound is a raw material, with the vanadium source compound, P source compound and Li source compound are pressed vanadium, phosphorus, the elemental lithium mol ratio is 2: 3: 3 a mixed, this mixture is at room temperature mixed, then add reducing agent, carry out mechanical activation then, soak time was controlled between 0.5～20 hour, the mol ratio of reducing agent and high price vanadium source compound is controlled between 1: 1～10: 1, under normal temperature and pressure conditions, incite somebody to action the reduction of high price vanadium and prepare the tiny unformed Li of particle with this reducing agent
3V
2(PO
4)
3, in non-oxidizing atmosphere, be heated to 500～700 ℃ then, and calcining at constant temperature 2～20 hours, make the phosphoric acid vanadium lithium powder of crystalline state.
2. the method for preparing cathode material lithium vanadium phosphate of lithium ion battery according to claim 1 is characterized in that: described high price vanadium source compound, select a kind of in vanadic oxide, vanadium dioxide, ammonium metavanadate, carbonic acid vanadium, the vanadium tetrachloride.
3. the method for preparing cathode material lithium vanadium phosphate of lithium ion battery according to claim 1, it is characterized in that: described P source compound, can select a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, phosphoric acid, phosphorus pentoxide, the diphosphorus trioxide.
4. the method for preparing cathode material lithium vanadium phosphate of lithium ion battery according to claim 1, it is characterized in that: described Li source compound, select a kind of in lithium carbonate, lithium formate, lithium hydroxide, lithium acetate, lithium fluoride, lithium iodide, lithia, lithium bromide, the lithium chloride.
5. the method for preparing cathode material lithium vanadium phosphate of lithium ion battery according to claim 1 is characterized in that: described reducing agent is selected a kind of in ascorbic acid, adipic acid, malonic acid, mandelic acid, ethanedioic acid, malic acid, lactic acid, citric acid, formaldehyde, acetaldehyde, hutanal, isobutylaldehyde, tetraethyl ethylene glycol, isopropyl alcohol, the ethylene glycol.
6. the method for preparing cathode material lithium vanadium phosphate of lithium ion battery according to claim 1 is characterized in that: described non-oxidizing gas is selected a kind of in argon gas, helium, neon, nitrogen, the hydrogen.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955176A (en) * | 2010-10-20 | 2011-01-26 | 河南联合新能源有限公司 | Method for preparing anode material lithium vanadium phosphate of lithium ion battery by microwave sintering |
| CN102244262A (en) * | 2011-05-19 | 2011-11-16 | 深圳科雷拉能源科技有限公司 | Composite anode material for lithium ion battery and preparation method thereof |
| CN102354752B (en) * | 2011-10-27 | 2014-04-16 | 中南大学 | Method used for preparing lithium ion battery positive pole material fluophosphate vanadium lithium |
| CN102364736A (en) * | 2011-11-11 | 2012-02-29 | 中南大学 | Method for preparing cathode material lithium vanadium fluorophosphates of lithium ion battery |
| CN104091953B (en) * | 2014-07-30 | 2016-06-15 | 中南大学 | Lithium ion battery negative material pyrophosphoric acid vanadium and preparation method thereof |
| CN104124455A (en) * | 2014-08-14 | 2014-10-29 | 中南大学 | Preparation method of three-dimensional interlayer lithium vanadium phosphate as anode material for lithium ion battery |
| CN104282891A (en) * | 2014-09-05 | 2015-01-14 | 中南大学 | Method for synthesizing lithium vanadium phosphate/carbon composite material by adopting one-step sol-gel method |
| CN108649223A (en) * | 2018-05-17 | 2018-10-12 | 攀枝花学院 | The preparation method of cathode material lithium vanadium phosphate of lithium ion battery |
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