CN104835960B - A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium - Google Patents
A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium Download PDFInfo
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- CN104835960B CN104835960B CN201510234376.3A CN201510234376A CN104835960B CN 104835960 B CN104835960 B CN 104835960B CN 201510234376 A CN201510234376 A CN 201510234376A CN 104835960 B CN104835960 B CN 104835960B
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium, comprises the following steps：（1）By vanadium source, phosphorus source, reducing agent according to v element, P elements and reducing agent mol ratio be 1:1:14 ratio is dissolved in deionized water；（2）Resulting solution is placed in 60-90 DEG C of water-bath and stirs 4 8h, solution is formed；（3）Resulting solution is adjusted into pH to 69；（4）Resulting solution granulate obtaining spherical fluorophosphoric acid vanadium presoma by the method for spray drying；（5）Gained fluorophosphoric acid vanadium presoma is placed in pipe type sintering furnace, in 400 800 DEG C of 6 15h of sintering under non-reducing atmosphere.The fluorophosphoric acid vanadium that the present invention is prepared first has the microcosmic spherical morphology of stable three-dimensional frame structure, quick particle conveying channels and uniqueness, shows excellent chemical property.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, more particularly, to one kind using spray drying
Technology prepares ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium（VPO4F）Method, belong to technical field of lithium ion.
Background technology
Negative material is as one of lithium ion battery critical material, and it studies the focus in the always field.At present, business
Graphite negative material is low due to its theoretical capacity（About 372mAh g-1）, metal oxide volumetric expansion during removal lithium embedded
Seriously, poorly reversible, these negative materials are difficult to the use requirement for meeting electrokinetic cell, therefore, explore other alternative new
Type negative material just seems particularly necessary.
The content of the invention
The technical problem to be solved in the present invention is to overcome the shortcomings of that existing negative material is high there is provided a kind of specific capacity, multiplying power
Performance is good, the preparation method of Stability Analysis of Structures and the lithium ion battery negative material fluorophosphoric acid vanadium having a safety feature, gained fluorophosphoric acid
The electrochemical performance of vanadium.
The present invention solve its technical problem use technical scheme be, a kind of lithium ion battery negative material fluorophosphoric acid vanadium
Preparation method, comprises the following steps：
（1）It is according to the mol ratio of v element, P elements, fluorine element and reducing agent by vanadium source, phosphorus source, Fluorine source, reducing agent
1:1:1:1-4 ratio is dissolved in deionized water, and the concentration for controlling metal vanadium ion is 0.05-1molL-1（It is preferred that 0.08-
0.8 mol·L-1, more preferably 0.1-0.5 molL-1, further preferred 0.2-0.4 molL-1）；
（2）By step（1）Gained mixed liquor, which is placed in 60-90 DEG C of water-bath, stirs 4-8h, forms solution；
（3）By step（2）Resulting solution adjusts pH to 6-9；
（4）By step（3）Granulation is dried by the method for spray drying in resulting solution, obtains fluorophosphoric acid vanadium
（VPO4F）Presoma；
（5）By step（4）Gained fluorophosphoric acid vanadium（VPO4F）Presoma is placed in pipe type sintering furnace, in non-reducing atmosphere
Lower 400-800 DEG C of sintering 6-20h（It is preferred that 8-15h）, room temperature is cooled to, ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium is obtained
（VPO4F）.
Further, step（1）In, the vanadium source is vanadic anhydride, ammonium metavanadate, ammonium vanadate, vanadyl acetylacetonate, grass
One kind in sour vanadyl.
Further, step（1）In, phosphorus source is one kind in phosphoric acid, phosphorus pentoxide, pyrophosphoric acid, ammonium phosphate.
Further, step（1）In, the Fluorine source is one kind in lithium fluoride, ammonium fluoride, sodium fluoride.
Further, step（1）In, the reducing agent be tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid,
One kind in ascorbic acid.
Further, step（4）In, the spray drying intake air temperature is spray-dried wriggling revolution speed at 180-260 DEG C
In 1000-1800rpm/min, spray drying rotation speed of fan is at 60-100 revs/min.
Further, step（5）In, the non-reducing atmosphere is argon gas, nitrogen or helium, or non-reducing gas and lazy
The mixed gas of property gas.
VPO4F space structure is by PO4Tetrahedron and VO4F2The space three-dimensional frame structure of octahedron composition.This three
Tie up in structure, VO4F2It is octahedra that zig-zag chains are formed by shared F ion in one-dimensional square and chain is extended, pass through
Shared PO4 3-Tetrahedral angle intersects chain, so as to form stable space three-dimensional structure.In VPO4In F, because F is to PO4 3-Compared with
Strong inductive effect, makes its structure more stablize；Therefore VPO4What F stablized as that can be provided during negative material for electrode material
Three-dimensional frame structure and quick particle conveying channels, crystal volume changes small, the safety of reinforcing material in charge and discharge process
Performance, quick particle conveying channels can increase the high rate performance of material.And because vanadium has active chemical property（V
To V5+）, VPO4F chemical valences in charge and discharge process can change from+4 to 0.Therefore, VPO4F has higher theoretical ratio
Capacity（650mAh/g）；And China's vanadium resource is abundant, raw material sources are extensively, with low cost.Therefore, VPO4F is a tool
There is the lithium ion battery negative material of very big potential value.
The present invention obtains spherical precursor by spray drying first, and synthesis obtains negative material fluorophosphoric acid vanadium；Follow-up
Non-reducing atmosphere in sintering obtain spherical fluorophosphoric acid vanadium negative material, because fluorophosphoric acid vanadium has stable three-dimensional framework knot
Structure, can provide for the deintercalation of lithium ion and stablize unobstructed passage, active active metallic element V can provide higher electric discharge
Specific capacity, as excellent chemical property can be shown during lithium ion battery negative material.
Brief description of the drawings
Fig. 1 is the SEM diffraction patterns of the gained ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium of the embodiment of the present invention 2；
Fig. 2 is existed using the assembled battery of 2 gained ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium institutes of the embodiment of the present invention
First charge-discharge curve map under 0.1C, 0.5C, 1C multiplying power.
Embodiment
The present invention is described in further detail below in conjunction with the drawings and specific embodiments.The embodiment of the present invention is used for providing
A further understanding of the present invention, is construed as limiting the invention for explaining the present invention, but not.
Embodiment 1
The present embodiment comprises the following steps：
（1）Vanadic anhydride 0.025mol, phosphoric acid 0.05mol, ammonium fluoride 0.05mol, ascorbic acid 0.2mol are weighed,
It is mixed, is dissolved in 1000mL deionized water；
（2）By step（1）Resulting solution is placed in mechanical agitation 5h in 80 DEG C of water-baths, forms uniform solution；
（3）By step（2）Resulting solution adjusts pH to 8；
（4）By step（3）Granulation, the spray drying is dried by the method for spray drying in resulting solution：Air intake
Mouth temperature is 250 DEG C, and wriggling revolution speed is 1400rpm/min, and rotation speed of fan is 100 revs/min, obtains VPO4F presomas；
（5）By step（4）Gained fluorophosphoric acid vanadium（VPO4F）Presoma is placed in pipe type sintering furnace, under an argon atmosphere in
700 DEG C of sintering 10h, are then naturally cooling to room temperature, obtain ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
The assembling of battery：Boric acid vanadium negative material obtained by 0.24g the present embodiment is weighed, adding 0.03g Super-P will
Above-mentioned material is assembled into CR2025 button cells, by battery surveyed in 0.01V~1.5V voltage ranges its charge/discharge capacity and times
Rate performance, test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power be followed successively by 651.3mAh/g, 436 mAh/g,
389.5mAh/g。
Embodiment 2
The present embodiment comprises the following steps：
（1）Vanadic anhydride 0.0125mol, phosphoric acid 0.025mol, sodium fluoride 0.025mol, oxalic acid 0.05mol are weighed, will
It is mixed, and is dissolved in 250mL deionized water；
（2）By step（1）Resulting solution is placed in mechanical agitation 8h in 60 DEG C of thermostat water baths, forms solution；
（3）By step（2）Resulting solution regulation pH is 7；
（4）By step（3）Granulation, the spray drying, air intake is dried by the method for spray drying in resulting solution
Mouth temperature is 260 DEG C, and wriggling revolution speed is 1000rpm/min, and rotation speed of fan is 60 revs/min, obtains VPO4F presomas；
（5）By step（4）Gained fluorophosphoric acid vanadium（VPO4F）Presoma is placed in pipe type sintering furnace, under an argon atmosphere in
700 DEG C of sintering 8h, are then naturally cooling to room temperature, obtain ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
Boric acid vanadium negative material obtained by the present embodiment is assembled into CR2025 button cells, by battery 0.01V~
Its charge/discharge capacity and high rate performance, test result ratio of electric discharge first under 0.1C, 0.5C, 1C multiplying power are surveyed in 1.5V voltage ranges
Capacity is followed successively by 609.5mAh/g, 382.2mAh/g, 289.9mAh/g.
The SEM diffraction patterns of ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium are as shown in Figure 1 obtained by the present embodiment；Use this
0.1C, 0.5C, 1C charge and discharge first for the battery that ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium prepared by embodiment is assembled
Electric curve is as shown in Figure 2.
Embodiment 3
The present embodiment comprises the following steps：
（1）Vanadic anhydride 0.04mol, ammonium phosphate 0.08mol, ammonium fluoride 0.08mol, ethanedioic acid 0.12mol are weighed, will
It is mixed, and is dissolved in 100mL deionized water；
（2）By step（1）Resulting solution is placed in mechanical agitation 6h in 80 DEG C of water-baths, forms uniform solution;
（3）By step（2）Resulting solution adjusts pH to 9；
（4）By step（3）Granulation, the spray drying is dried by the method for spray drying in resulting solution：Air intake
Mouth temperature is 200 DEG C, and wriggling revolution speed is 1500rpm/min, and rotation speed of fan is 100 revs/min, obtains VPO4F presomas；
（5）By step（4）Gained fluorophosphoric acid vanadium（VPO4F）Presoma is placed in pipe type sintering furnace, in a nitrogen atmosphere in
500 DEG C of sintering 20h, are then naturally cooling to room temperature, obtain ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
Lithium ion battery negative material fluorophosphoric acid vanadium obtained by the present embodiment is assembled into CR2025 button cells, battery is existed
Its charge/discharge capacity and high rate performance are surveyed in 0.01V~1.5V voltage ranges, test result is first under 0.1C, 0.5C, 1C multiplying power
Secondary specific discharge capacity is followed successively by 451.3mAh/g, 277.6mAh/g, 239.8mAh/g.
Embodiment 4
The present embodiment comprises the following steps：
（1）Weigh ammonium metavanadate 0.01mol, phosphorus pentoxide 0.005mol, sodium fluoride 0.01mol, citric acid
0.04mol, is mixed, and is dissolved in 200mL deionized water；
（2）By step（1）Resulting solution is placed in mechanical agitation 4h in 90 DEG C of thermostat water baths, forms uniform solution；
（3）By step（2）Resulting solution adjusts pH to 6；
（4）By step（3）Granulation, the spray drying is dried by the method for spray drying in resulting solution：Air intake
Mouth temperature is 180 DEG C, and wriggling revolution speed is 1800rpm/min, and rotation speed of fan obtains to be spray-dried under 80 revs/min
VPO4F presomas；
（5）By step（4）Gained fluorophosphoric acid vanadium（VPO4F）Presoma is placed in pipe type sintering furnace, under an argon atmosphere in
800 DEG C of sintering 8h, are then naturally cooling to room temperature, obtain ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
Above-mentioned material is assembled into CR2025 button cells, battery is surveyed into its charge and discharge in 0.01V~1.5V voltage ranges
Capacitance and high rate performance, test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power be followed successively by 589.1mAh/g,
305.2mAh/g、289.5mAh/g。
Embodiment 5
The present embodiment comprises the following steps：
（1）Vanadyl acetylacetonate 0.1mol, phosphoric acid 0.1mol, lithium fluoride 0.1mol, oxalic acid 0.3mol are weighed, is mixed
Close, be dissolved in 100mL deionized water；
（2）By step（1）Resulting solution is placed in mechanical agitation 6h in 70 DEG C of water-baths, forms uniform solution；
（3）By step（2）Resulting solution adjusts pH to 7；
（4）By step（3）Granulation, the spray drying is dried by the method for spray drying in resulting solution：Air intake
Mouth temperature is 240 DEG C, and wriggling revolution speed is 1100rpm/min, and rotation speed of fan is 80 revs/min, obtains VPO4F presomas；
（5）By step（4）Gained fluorophosphoric acid vanadium（VPO4F）Presoma is placed in pipe type sintering furnace, under an argon atmosphere in
650 DEG C of sintering 10h, are then naturally cooling to room temperature, obtain ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
Above-mentioned material is assembled into CR2025 button cells, battery is surveyed into its charge and discharge in 0.01V~1.5V voltage ranges
Capacitance and high rate performance, test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power be followed successively by 591.5mAh/g,
482.2mAh/g、399.4mAh/g。
The fluorophosphoric acid prepared by the present invention is can be seen that more than（VPO4F）Negative material, for assembled battery, institute
The charging and discharging capacity for obtaining battery is higher, and high rate performance is good.The negative material graphite institute used with the B of CN 102110813
The battery being assembled into compares, and its highest first discharge specific capacity under 0.1C multiplying powers is only 360.9mAh/g, far smaller than
Fluorophosphoric acid vanadium negative material prepared by the present invention.Therefore, it can be seen that the lithium ion battery negative material prepared by the present invention
Fluorophosphoric acid vanadium（VPO4F）It is a kind of novel cathode material for lithium ion battery of excellent performance.
Claims (9)
1. a kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium, it is characterised in that comprise the following steps：
（1）By vanadium source, phosphorus source, Fluorine source, reducing agent according to v element, P elements, fluorine element and reducing agent mol ratio be 1:1:
1:1-4 ratio is dissolved in deionized water, and the concentration for controlling metal vanadium ion is 0.05-1molL-1；
（2）By step（1）Gained mixed liquor, which is placed in 60-90 DEG C of water-bath, stirs 4-8h, forms solution；
（3）By step（2）Resulting solution adjusts pH to 6-9；
（4）By step（3）Granulation is dried by the method for spray drying in resulting solution, obtains fluorophosphoric acid vanadium presoma；
（5）By step（4）Gained fluorophosphoric acid vanadium presoma is placed in pipe type sintering furnace, in 400-800 DEG C under non-reducing atmosphere
6-20h is sintered, room temperature is cooled to, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
2. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1, it is characterised in that step
（1）In, the concentration for controlling metal vanadium ion is 0.08-0.8 molL-1。
3. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 2, it is characterised in that control
The concentration of metal vanadium ion is 0.1-0.5 molL-1。
4. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 3, it is characterised in that control
The concentration of metal vanadium ion is 0.2-0.4 molL-1。
5. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 or 2, it is characterised in that
Step（1）In, the vanadium source is one kind in vanadic anhydride, ammonium metavanadate, ammonium vanadate, vanadyl acetylacetonate, vanadyl oxalate；
Phosphorus source is one kind in phosphoric acid, phosphorus pentoxide, pyrophosphoric acid, ammonium phosphate；The Fluorine source is lithium fluoride, ammonium fluoride, fluorination
One kind in sodium.
6. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 or 2, it is characterised in that
Step（1）In, the reducing agent is one in tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid, ascorbic acid
Kind.
7. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 or 2, it is characterised in that
Step（4）In, the spray drying intake air temperature is at 180-260 DEG C, and spray drying wriggling revolution speed is in 1000-1800rpm/
Min, spray drying rotation speed of fan is at 60-100 revs/min.
8. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 or 2, it is characterised in that
Step（5）In, the non-reducing atmosphere is argon gas, nitrogen or helium.
9. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 or 2, it is characterised in that
Step（6）In, the sintering time is 8-15h.
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| CN102079517A (en) * | 2009-11-29 | 2011-06-01 | 宁波大学 | Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method |
| CN102386407A (en) * | 2011-11-02 | 2012-03-21 | 中南大学 | Method for preparing anode material lithium vanadium phosphate by adopting quenching |
| CN103864045A (en) * | 2014-03-28 | 2014-06-18 | 张宝 | Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4 |
| CN103872324A (en) * | 2014-03-28 | 2014-06-18 | 郑俊超 | Preparation method of petaloid lithium ion battery negative electrode material VPO4 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079517A (en) * | 2009-11-29 | 2011-06-01 | 宁波大学 | Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method |
| CN102386407A (en) * | 2011-11-02 | 2012-03-21 | 中南大学 | Method for preparing anode material lithium vanadium phosphate by adopting quenching |
| CN103864045A (en) * | 2014-03-28 | 2014-06-18 | 张宝 | Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4 |
| CN103872324A (en) * | 2014-03-28 | 2014-06-18 | 郑俊超 | Preparation method of petaloid lithium ion battery negative electrode material VPO4 |
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