CN103864045A - Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4 - Google Patents
Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4 Download PDFInfo
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- CN103864045A CN103864045A CN201410120024.0A CN201410120024A CN103864045A CN 103864045 A CN103864045 A CN 103864045A CN 201410120024 A CN201410120024 A CN 201410120024A CN 103864045 A CN103864045 A CN 103864045A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a freeze drying method of preparing a porous channel-shaped lithium ion battery negative electrode material, namely vanadium phosphate, and belongs to the technical field of lithium ion batteries. The method is characterized in that the lithium ion battery negative electrode material, namely vanadium phosphate is prepared by adopting a freeze drying technology. The method comprises the following specific steps: dissolving a vanadium source, a phosphorus source and a reducing agent in water in a molar stoichiometric ratio being 1: 1: 3, and stirring so as to obtain a uniform solution; transferring the obtained uniform solution to a vacuum freeze drying cabinet, and carrying out freeze drying at the temperature of -40 DEG C and the pressure of 15Pa till obtaining precursor dry powder of vanadium phosphate; grinding, tabletting, putting the precursor in a tubular sintering furnace, sintering at the temperature of 750 DEG C in a non-oxidizing atmosphere for 6 hours, and cooling to room temperature so as to obtain the negative electrode material, namely vanadium phosphate. The VPO4 negative electrode material is prepared by adopting the vacuum freeze drying technology; the preparation process is simple, and operation is easy; the morphology of the obtained material is of a porous structure; the material has excellent electrochemical capacity; the freeze drying technology is a new method for preparing the lithium ion battery negative electrode material VPO4.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, specifically a kind of Freeze Drying Technique that adopts is prepared a kind of duct shape lithium ion battery negative material VPO
4method.Belong to technical field of lithium ion.
Background technology
Since lithium ion battery is born, the negative material of research mainly contains graphitized carbon negative pole, amorphous carbon material, nitride, silica-base material, tin-based material, novel alloy, nano-oxide etc., in numerous negative materials, have that redox potential is low, specific storage is high, Stability Analysis of Structures, raw material cheapness, free of contamination negative pole matrix are that investigator pursues always.And polyanion metal-salt is because it can provide good structural stability compared with large polyanion group, its three-dimensional frame structure provides unobstructed reversible deintercalation passage for lithium ion.Wherein VPO
4negative material is except having above advantage, and the chemical activity of vanadium, can provide higher specific storage, and China's vanadium resource is abundant, and starting material wide material sources are with low cost.Therefore, VPO
4to there is very large researching value as negative material.
The present invention has synthesized the VPO with pore passage structure by Freeze Drying Technique
4negative material, the material pattern of synthesized is special, shows excellent chemical property.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing Freeze Drying Technique to prepare duct shape lithium ion battery negative material vanadium phosphate, to improve lithium ion battery negative material vanadium phosphate chemical property.
Technical scheme of the present invention is as follows:
(1) vanadium source, phosphorus source are mixed with the mol ratio of vanadium ion, phosphate anion at 1: 1, add the organic carbon source of 3 times of lithium source mole numbers as reactant feed simultaneously, mechanical stirring is to forming uniform solution, and concentration of metal ions is controlled at 0.005-2mol/L.
(2) above-mentioned solution is transferred in vacuum freeze drier ,-40 DEG C, 15Pa lyophilize obtain vanadium phosphorus oxide lithium presoma;
(3) above-mentioned presoma is taken out through grinding, compressing tablet and is placed in pipe type sintering furnace, in lower 600 DEG C～800 DEG C sintering 1-20H of nonoxidizing atmosphere, cool to room temperature obtains vanadium phosphate negative material;
Further, the vanadium source described in step (1) is Vanadium Pentoxide in FLAKES, ammonium meta-vanadate, ammonium vanadate, vanadous oxide, oxalic acid vanadyl one;
Further, the phosphorus source described in step (1) is the one in primary ammonium phosphate, phosphorus hydrogen two ammoniums, ammonium phosphate, phosphoric acid, tetra-sodium;
Further, the reductive agent described in step (1) is the one in tartrate, citric acid, oxalic acid, oxalic acid, hexanodioic acid, propanedioic acid, xitix;
Further, the condenser temperature when freeze drier described in step (2) is freezing is-10 DEG C～-50 DEG C;
Further, the vacuum tightness when freeze drier freeze drier lyophilize described in step (2) is 5Pa～30Pa;
Further, in step (3), the nonoxidizing atmosphere of sintering is the one in argon gas, nitrogen, hydrogen, helium, carbon monoxide;
Advantage of the present invention:
The present invention utilizes Freeze Drying Technique to prepare duct shape lithium ion battery negative material VPO
4.The negative pole utmost point material preparing is loose porous VPO
4thin, its vesicular structure is conducive to wetting to material of electrolytic solution, has reduced lithium ion transport resistance; The activity that higher specific surface area has increased lithium ion embeds site; And good surface tissue, can make material and ionogen form good SEI film.Above advantage all contributes to improve the chemical property of material.
Brief description of the drawings
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, for explaining the present invention, is not construed as limiting the invention together with embodiments of the present invention.In the accompanying drawings:
Fig. 1 is the XRD figure of No. 3 samples in embodiment 1;
Fig. 2 is the SEM diffractogram of No. 3 sample presomas in embodiment 1;
Fig. 3 is 0.1C, 0.5C, the 1C discharge curve first of No. 3 samples in embodiment 1;
Embodiment
Embodiment 1
Take Vanadium Pentoxide in FLAKES 1.82g, Secondary ammonium phosphate 2.3g, citric acid 4.2g, is dissolved in the deionized water of 300mL, and mechanical stirring is to forming uniform solution; Then gone in freeze drier-40 DEG C, 15Pa lyophilize to the presoma dry powder that obtains vanadium phosphate.Vanadium phosphate presoma is fully ground in agate mortar, be then placed in sintering oven, under argon gas atmosphere, in 600 DEG C, 700 DEG C, 750 DEG C, 800 DEG C sintering 6h, be then naturally cooled to room temperature and obtain vanadium phosphate.Products obtained therefrom wherein obtains pure phase VPO at 700 DEG C, 750 DEG C through XRD analysis
4, at other temperature, products obtained therefrom has VPO
4.xH
2o or V
2o
5dephasign.Detect by SEM, the microscopic appearance of 1,2, No. 3 resulting materials is pore passage structure.Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, carry out charge-discharge test under 0.1C, 0.5C, 1C, its first discharge specific capacity is in table 1.
The experiment condition of table 1 experimental example 1 and experimental result
Embodiment 2
Take Vanadium Pentoxide in FLAKES 1.82g, Secondary ammonium phosphate 2.3g, citric acid 4.2g, is dissolved in the deionized water of 300mL, and mechanical stirring is to forming uniform solution; Then gone in freeze drier-40 DEG C, 15Pa lyophilize to obtaining vanadium phosphate presoma dry powder.Vanadium phosphate presoma is fully ground in agate mortar, is then placed in sintering oven, under argon gas atmosphere in 750 DEG C of sintering 2h, 4h, 8h, then 10h is naturally cooled to room temperature and obtains vanadium phosphate.Products obtained therefrom is all pure phase VPO through XRD analysis
4, detecting by SEM, the microscopic appearance of 1, No. 2 resulting materials is pore passage structure, and the pore passage structure of 3, No. 4 resulting materials is broken into fragment.Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, carry out charge-discharge test under 0.1C, 0.5C, 1C, its first discharge specific capacity is in table 2.
The experiment condition of table 2 experimental example 2 and experimental result
Embodiment 3
Take Vanadium Pentoxide in FLAKES 1.82g, Secondary ammonium phosphate 2.3g, citric acid 4.2g, is dissolved in the deionized water of 300mL, and mechanical stirring is to forming uniform solution; Then gone in freeze drier-50 DEG C ,-30 DEG C ,-20 DEG C ,-10 DEG C, 15Pa lyophilize is to obtaining vanadium phosphate presoma dry powder.Vanadium phosphate presoma is fully ground in agate mortar, be then placed in sintering oven, under argon gas atmosphere, be then naturally cooled to room temperature in 750 DEG C of sintering 6h and obtain vanadium phosphate.Products obtained therefrom is pure phase VPO through No. 2 samples of XRD analysis
4, detect by SEM, only have the microscopic appearance of No. 2 resulting materials to be pore passage structure.Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, carry out charge-discharge test under 0.1C, 0.5C, 1C, its first discharge specific capacity is in table 3.
The experiment condition of table 3 experimental example 3 and experimental result
Claims (8)
1. a preparation method for duct shape lithium ion battery negative material vanadium phosphate, is characterized in that comprising the following steps:
(1) vanadium source, phosphorus source are mixed with the mol ratio of vanadium ion, phosphate anion at 1: 1, add the organic carbon source of 3 times of lithium source mole numbers as reactant feed simultaneously, mechanical stirring is to forming uniform solution, and concentration of metal ions is controlled at 0.005-2mol/L;
(2) above-mentioned solution is transferred in vacuum freeze drier ,-40 DEG C, 15Pa lyophilize obtain vanadium phosphorus oxide lithium presoma;
(3) above-mentioned presoma is taken out through grinding, compressing tablet and is placed in pipe type sintering furnace, in lower 600 DEG C～800 DEG C sintering 1-20H of nonoxidizing atmosphere, cool to room temperature obtains vanadium phosphate negative material.
2. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method, it is characterized in that: vanadium source, phosphorus source are mixed by mole proportioning with reductive agent at 1: 1: 3, and vanadium metal ionic concn is controlled at 0.005-2mol L
-1between.
3. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method, it is characterized in that: in step (1), described vanadium source is the one in Vanadium Pentoxide in FLAKES, ammonium meta-vanadate, ammonium vanadate, vanadous oxide, oxalic acid vanadyl.
4. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method, it is characterized in that: in step (1), described phosphorus source is the one in primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate, phosphoric acid, tetra-sodium.
5. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method it is characterized in that:, in step (1), described reductive agent is the one in tartrate, citric acid, oxalic acid, oxalic acid, hexanodioic acid, propanedioic acid, xitix.
6. a kind of lithium ion battery negative material VPO according to claim 1
4preparation method it is characterized in that: the one in argon gas that the nonoxidizing atmosphere of sintering is, nitrogen, hydrogen, helium, carbon monoxide.
7. the preparation method of a kind of lithium ion battery negative material vanadium phosphate according to claim 1, is characterized in that: condenser temperature when freeze drier is freezing is-10 DEG C～-50 DEG C.
8. the preparation method of a kind of lithium ion battery negative material vanadium phosphate according to claim 1, is characterized in that: vacuum tightness when freeze drier lyophilize is 5Pa～30Pa.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104091953A (en) * | 2014-07-30 | 2014-10-08 | 中南大学 | Lithium ion battery negative material-vanadium pyrophosphate and preparation method thereof |
| CN104124440A (en) * | 2014-07-28 | 2014-10-29 | 中南大学 | Method for preparing porous spherical positive electrode material (lithium vanadium pyrophosphate) for lithium ion battery |
| CN104835960A (en) * | 2015-05-08 | 2015-08-12 | 中南大学 | Preparation method for lithium ion battery cathode material VPO4F |
| CN105129758A (en) * | 2015-06-30 | 2015-12-09 | 中南大学 | Porous manganese vanadium lithium lithium phosphate composite cathode material and preparation method thereof |
| CN107230771A (en) * | 2017-07-14 | 2017-10-03 | 中南大学 | A kind of method of vanadium phosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium |
| CN108461751A (en) * | 2018-03-31 | 2018-08-28 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of mesoporous vanadium phosphate cathode material |
| EP3314686A4 (en) * | 2015-06-26 | 2019-08-07 | A123 Systems LLC | Nanoscale pore structure cathode for high power applications and material synthesis methods |
| CN111072002A (en) * | 2019-12-20 | 2020-04-28 | 大连博融新材料有限公司 | Vanadium phosphate, preparation method thereof and application thereof in lithium ion battery anode material |
Citations (2)
| 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 |
| CN102774821A (en) * | 2012-07-30 | 2012-11-14 | 四川大学 | Solid phase-hydrothermal preparation method for lithium vanadium phosphate |
-
2014
- 2014-03-28 CN CN201410120024.0A patent/CN103864045B/en active Active
Patent Citations (2)
| 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 |
| CN102774821A (en) * | 2012-07-30 | 2012-11-14 | 四川大学 | Solid phase-hydrothermal preparation method for lithium vanadium phosphate |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104124440A (en) * | 2014-07-28 | 2014-10-29 | 中南大学 | Method for preparing porous spherical positive electrode material (lithium vanadium pyrophosphate) for lithium ion battery |
| CN104091953A (en) * | 2014-07-30 | 2014-10-08 | 中南大学 | Lithium ion battery negative material-vanadium pyrophosphate and preparation method thereof |
| CN104835960B (en) * | 2015-05-08 | 2017-08-25 | 中南大学 | A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium |
| CN104835960A (en) * | 2015-05-08 | 2015-08-12 | 中南大学 | Preparation method for lithium ion battery cathode material VPO4F |
| EP3314686A4 (en) * | 2015-06-26 | 2019-08-07 | A123 Systems LLC | Nanoscale pore structure cathode for high power applications and material synthesis methods |
| EP3677543A1 (en) * | 2015-06-26 | 2020-07-08 | A123 Systems LLC | Nanoscale pore structure cathode for high power applications and material synthesis methods |
| US11088389B2 (en) | 2015-06-26 | 2021-08-10 | A123 Systems Llc | Nanoscale pore structure cathode for high power applications and material synthesis methods |
| CN113651302A (en) * | 2015-06-26 | 2021-11-16 | A123系统有限责任公司 | Method for synthesizing vanadium phosphate |
| US11916185B2 (en) | 2015-06-26 | 2024-02-27 | A123 Systems Llc | Nanoscale pore structure cathode for high power applications and material synthesis methods |
| CN105129758B (en) * | 2015-06-30 | 2017-12-19 | 中南大学 | A kind of porous calcium phosphate manganese vanadium lithium composite positive pole and preparation method thereof |
| CN105129758A (en) * | 2015-06-30 | 2015-12-09 | 中南大学 | Porous manganese vanadium lithium lithium phosphate composite cathode material and preparation method thereof |
| CN107230771A (en) * | 2017-07-14 | 2017-10-03 | 中南大学 | A kind of method of vanadium phosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium |
| CN107230771B (en) * | 2017-07-14 | 2020-08-14 | 中南大学 | Method for coating lithium ion battery cathode material nickel cobalt lithium manganate with vanadium phosphate |
| CN108461751A (en) * | 2018-03-31 | 2018-08-28 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of mesoporous vanadium phosphate cathode material |
| CN108461751B (en) * | 2018-03-31 | 2022-10-11 | 广东天劲新能源科技股份有限公司 | Preparation method of mesoporous lithium vanadium phosphate cathode material |
| CN111072002A (en) * | 2019-12-20 | 2020-04-28 | 大连博融新材料有限公司 | Vanadium phosphate, preparation method thereof and application thereof in lithium ion battery anode material |
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