CN103864045B - A kind of duct shape lithium ion battery negative material VPO4preparation method - Google Patents
A kind of duct shape lithium ion battery negative material VPO4preparation method Download PDFInfo
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- CN103864045B CN103864045B CN201410120024.0A CN201410120024A CN103864045B CN 103864045 B CN103864045 B CN 103864045B CN 201410120024 A CN201410120024 A CN 201410120024A CN 103864045 B CN103864045 B CN 103864045B
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Abstract
The invention discloses a kind of method that freeze-drying prepares duct shape lithium ion battery negative material vanadium phosphate, belong to technical field of lithium ion.It is characterized in that: use Freeze Drying Technique to prepare lithium ion battery negative material vanadium phosphate.Specifically include following steps: by more soluble in water than vanadium source, phosphorus source and the reducing agent being 1: 1: 3 for mole metering, stirring obtains homogeneous solution；Obtained solution is transferred in vacuum freezing drying oven by solution homogeneous for gained, 40 DEG C, 15Pa lyophilization is to the presoma dry powder obtaining vanadium phosphate.Ground, tabletting, is placed in presoma in pipe type sintering furnace, in the lower 750 DEG C of sintering 6H of nonoxidizing atmosphere, is cooled to room temperature and obtains vanadium phosphate negative pole pole material.The present invention prepares VPO by the technology of vacuum lyophilization4Negative material, preparation process is simple, easily operates, and resulting materials pattern is pore passage structure, and material list reveals the electrochemistry of excellence, and Freeze Drying Technique is lithium ion battery negative material VPO4A kind of new method of preparation.
Description
Technical field
The present invention relates to the preparation method of a kind of lithium ion battery negative material, specifically a kind of employing a kind of duct shape lithium ion battery negative material VPO of Freeze Drying Technique preparation4Method.Belong to technical field of lithium ion.
Background technology
Since lithium ion battery is born, the negative material of research mainly has 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 oxidation-reduction potential is low, specific capacity is high, Stability Analysis of Structures, cheaper starting materials, free of contamination negative pole matrix are always what researcher was pursued.And polyanjionic metal salt can provide preferable structural stability due to its bigger polyanion group, its three-dimensional frame structure provides unobstructed reversible deintercalation passage for lithium ion.Wherein VPO4Negative material is in addition to having above advantage, and the chemical activity of vanadium, using the teaching of the invention it is possible to provide higher specific capacity, and China's vanadium resource enriches, raw material sources is extensive, with low cost.Therefore, VPO4It is that there is the biggest researching value as negative material.
The present invention has synthesized the VPO with pore passage structure by Freeze Drying Technique4Negative material, synthesized material morphology is special, shows the chemical property of excellence.
Summary of the invention
It is an object of the invention to provide a kind of method 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 is as follows:
(1) vanadium source, phosphorus source being mixed with the mol ratio 1: 1 of vanadium ion, phosphate anion, be simultaneously introduced the organic carbon source of lithium source molal quantity 3 times as reactant feed, mechanical agitation is to forming uniform solution, and concentration of metal ions controls at 0.005-2mol/L.
(2) above-mentioned solution is transferred in vacuum freeze drier ,-40 DEG C, 15Pa lyophilization obtain vanadyl phosphate lithium presoma；
(3) ground for the taking-up of above-mentioned presoma, tabletting are placed in pipe type sintering furnace, in lower 600 DEG C～the 800 DEG C sintering 1-20H of nonoxidizing atmosphere, are cooled to room temperature and obtain vanadium phosphate negative material；
Further, the vanadium source described in step (1) is vanadic anhydride, ammonium metavanadate, ammonium vanadate, Vanadium sesquioxide, vanadyl oxalate one；
Further, the one during the phosphorus source described in step (1) is ammonium dihydrogen phosphate, phosphorus hydrogen diammonium, ammonium phosphate, phosphoric acid, pyrophosphoric acid；
Further, the reducing agent described in step (1) is the one in tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid, ascorbic acid；
Further, condenser temperature during freezer dryer freezing described in step (2) is-10 DEG C～-50 DEG C；
Further, vacuum during freezer dryer freezer dryer lyophilization described in step (2) is 5Pa～30Pa；
Further, in step (3), the nonoxidizing atmosphere of sintering is the one in argon, nitrogen, hydrogen, helium, carbon monoxide；
Advantages of the present invention:
The present invention utilizes Freeze Drying Technique to prepare duct shape lithium ion battery negative material VPO4.The negative pole pole material prepared is loose porous VPO4Thin piece, its loose structure is conducive to the electrolyte moistening to material, decreases lithium ion transport resistance；Higher specific surface area adds the activity of lithium ion and embeds site；And good surface texture, it is possible to make material and electrolyte form good SEI film.Above advantage both contributes to improve the chemical property of material.
Accompanying drawing explanation
Accompanying drawing is for providing a further understanding of the present invention, and constitutes a part for description, is used for together with embodiments of the present invention explaining the present invention, is not intended that limitation 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 diffraction pattern of No. 3 sample presomas in embodiment 1；
Fig. 3 is 0.1C, 0.5C, 1C of No. 3 samples discharge curve first in embodiment 1；
Detailed description of the invention
Embodiment 1
Weighing vanadic anhydride 1.82g, diammonium phosphate 2.3g, citric acid 4.2g, be dissolved in the deionized water of 300mL, mechanical agitation is to forming uniform solution；Then gone in freezer dryer-40 DEG C, 15Pa lyophilization is to the presoma dry powder obtaining vanadium phosphate.Vanadium phosphate presoma is fully ground in agate mortar, is subsequently placed in sintering furnace, under an argon atmosphere in 600 DEG C, 700 DEG C, 750 DEG C, 800 DEG C of sintering 6h, be then naturally cooling to room temperature and obtain vanadium phosphate.Products obtained therefrom wherein obtains pure phase VPO at 700 DEG C, 750 DEG C through XRD analysis4, at a temperature of other, products obtained therefrom has VPO4.xH2O or V2O5Dephasign.Being detected by SEM, the microscopic appearance of 1,2, No. 3 resulting materials is pore passage structure.Obtained product being 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 shown in Table 1.
The experiment condition of table 1 experimental example 1 and experimental result
Embodiment 2
Weighing vanadic anhydride 1.82g, diammonium phosphate 2.3g, citric acid 4.2g, be dissolved in the deionized water of 300mL, mechanical agitation is to forming uniform solution；Then gone in freezer dryer-40 DEG C, 15Pa lyophilization is to obtaining vanadium phosphate presoma dry powder.Being fully ground in agate mortar by vanadium phosphate presoma, be subsequently placed in sintering furnace, sinter 2h in 750 DEG C under an argon atmosphere, then 4h, 8h, 10h are naturally cooling to room temperature and obtain vanadium phosphate.Products obtained therefrom is all pure phase VPO through XRD analysis4, being detected 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 being 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 shown in Table 2.
The experiment condition of table 2 experimental example 2 and experimental result
Embodiment 3
Weighing vanadic anhydride 1.82g, diammonium phosphate 2.3g, citric acid 4.2g, be dissolved in the deionized water of 300mL, mechanical agitation is to forming uniform solution；Then being gone in freezer dryer-50 DEG C ,-30 DEG C ,-20 DEG C ,-10 DEG C, 15Pa lyophilization is to obtaining vanadium phosphate presoma dry powder.Vanadium phosphate presoma is fully ground in agate mortar, is subsequently placed in sintering furnace, be then naturally cooling to room temperature in 750 DEG C of sintering 6h under an argon atmosphere and obtain vanadium phosphate.Products obtained therefrom is pure phase VPO through No. 2 samples of XRD analysis4, being detected by SEM, the only microscopic appearance of No. 2 resulting materials is pore passage structure.Obtained product being 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 shown in Table 3.
The experiment condition of table 3 experimental example 3 and experimental result
Claims (4)
1. the preparation method of a duct shape lithium ion battery negative material vanadium phosphate, it is characterised in that: comprise the following steps
:
(1) by vanadium source, phosphorus source and organic carbon source with the mol ratio 1:1:3 mixing of phosphate anion and organic carbon source in vanadium ion, phosphorus source in vanadium source, mechanical agitation is to forming uniform solution, and concentration of metal ions controls 0.005～2mol/L；Described organic carbon source is the one in tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid, ascorbic acid；
(2) above-mentioned solution is transferred in vacuum freeze drier ,-40 DEG C, 15Pa lyophilization obtain vanadium phosphate presoma；
(3) ground for the taking-up of above-mentioned presoma, tabletting being placed in pipe type sintering furnace, under nonoxidizing atmosphere, 600～800 DEG C of sintering 1～20h, are cooled to room temperature and obtain vanadium phosphate negative material.
The preparation method of a kind of duct the most according to claim 1 shape lithium ion battery negative material vanadium phosphate, it is characterized in that: in step (1), described vanadium source is the one in vanadic anhydride, ammonium metavanadate, ammonium vanadate, Vanadium sesquioxide, vanadyl oxalate.
The preparation method of a kind of duct the most according to claim 1 shape lithium ion battery negative material vanadium phosphate, it is characterised in that: in step (1), described phosphorus source is the one in ammonium dihydrogen phosphate, diammonium phosphate, ammonium phosphate, phosphoric acid, pyrophosphoric acid.
The preparation method of a kind of duct the most according to claim 1 shape lithium ion battery negative material vanadium phosphate, it is characterised in that: the nonoxidizing atmosphere of sintering is the one in argon, nitrogen, hydrogen, helium, carbon monoxide.
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| CN104124440B (en) * | 2014-07-28 | 2017-01-25 | 中南大学 | Method for preparing porous spherical positive electrode material (lithium vanadium pyrophosphate) for 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 |
| 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 |
| KR102621149B1 (en) * | 2015-06-26 | 2024-01-04 | 에이일이삼 시스템즈 엘엘씨 | Methods for synthesizing nanoscale pore structured cathodes and materials for high power applications |
| 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 |
| 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 |
| 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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| CN102774821B (en) * | 2012-07-30 | 2014-05-21 | 四川大学 | Solid phase-hydrothermal preparation method for lithium vanadium phosphate |
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