CN101315979A - Method for producing lithium ion battery anode material vanadium lithium phosphate by sol-gel method - Google Patents

Method for producing lithium ion battery anode material vanadium lithium phosphate by sol-gel method Download PDF

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Publication number
CN101315979A
CN101315979A CNA2008100736791A CN200810073679A CN101315979A CN 101315979 A CN101315979 A CN 101315979A CN A2008100736791 A CNA2008100736791 A CN A2008100736791A CN 200810073679 A CN200810073679 A CN 200810073679A CN 101315979 A CN101315979 A CN 101315979A
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China
Prior art keywords
lithium
phosphate
vanadium
gel
acid
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CNA2008100736791A
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钟胜奎
王健
刘乐通
刘洁群
姜吉琼
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Guilin University of Technology
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Guilin University of Technology
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Priority to CNA2008100736791A priority Critical patent/CN101315979A/en
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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

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Abstract

The invention discloses a method for preparing lithium ion battery anode material vanadium lithium phosphoric acid by a sol-gel method. The method of the invention comprises the following steps: the vanadium pentoxide powder is heated to 600-900 DEG C and the temperature is kept for 1-4 hours till the power is melted; the melted powder is rapidly dumped into a container with water to form a brownish red solution; subsequently, lithium salt, phosphate and organic acid are added into the solution; the solution is uniformly mixed and then sintered for 5-20 hours under the protection of inert gas so as to form a finished product LI3V2(PO4)3 after being cooled. The method of the invention solves the problem that the vanadium ion is easy to be oxidated, the sintering temperature and the cost are reduced, and the charging and discharging performance and the circulation performance of the samples are improved.

Description

Sol-gel process prepares the method for cathode material lithium vanadium phosphate of lithium ion battery
Technical field
The present invention relates to the method that a kind of sol-gel process prepares cathode material lithium vanadium phosphate of lithium ion battery.
Background technology
Li 3V 2(PO 4) 3It is good that material has a reversibility, the advantages such as abundant raw materials, specific capacity height (theoretical capacity is 197mAh/g).But it has following shortcoming and has hindered its practical application: V during (1) is synthetic 3+Easily be oxidized to V 5+, be difficult to obtain single-phase Li 3V 2(PO 4) 3(2) lithium ion is at Li 3V 2(PO 4) 3Middle diffusion difficulty causes the utilization rate of active material low; (3) Li 3V 2(PO 4) 3The electrical conductivity of itself is also very low, causes its heavy-current discharge performance poor.Existing research improves Li by following several respects 3V 2(PO 4) 3Performance: (1) adopts inert atmosphere to protect V 3+(2) Li of synthetic small particle diameter 3V 2(PO 4) 3Improve the insertion of lithium ability; (3) add conductive agent and improve electrical conductivity.Bibliographical information synthesizes Li at present 3V 2(PO 4) 3Material mainly adopts hydrogen reduction method and pyrocarbon thermal reduction.Hydrogen reduction method is owing to adopt pure H 2As reducing agent, when experimental implementation because H 2Inflammable and explosive character and very dangerous, be unfavorable for suitability for industrialized production.And shortcoming such as the skewness of institute's synthetic material particle diameter and electric conductivity be low.The pyrocarbon thermal reduction since the reaction temperature that needs than higher, thereby the material particle size skewness, electric conductivity and the cycle performance that are synthesized are bad.
Summary of the invention
The object of the present invention is to provide a kind of employing sol-gel process to prepare anode material for lithium-ion batteries Li 3V 2(PO 4) 3Method.To solve the easy oxidation of vanadium ion, to make that institute's synthetic material particle size distribution is even, tiny, conductivity improves, reduce sintering temperature, reduce cost, improved the chemical property of sample, simplified technology, make it to be easy to industrialized purpose.
Technical scheme of the present invention may further comprise the steps:
(1) vanadium pentoxide powder is heated to 600-900 ℃, and constant temperature 1-4h makes to pour into rapidly in the container that water is housed after its melting and form brown-red solution, this solution left standstill 4-16h can form V 2O 5NH 2The O wet gel; With removing most of moisture after the wet gel washing, then at 70-100 ℃ of lower vacuum drying 4-16h, grind and obtain the pentoxide gel powder;
(2) the above-mentioned pentoxide gel powder for preparing and lithium salts, phosphate, organic acid are 0.95-1.05: 2.9-3.1: 2.9-3.1 in molar ratio: after 0.95-1.05 mixes; under the protection of inert gas, in 400 ℃ of-700 ℃ of sintering 5-20h, be finished product Li after the cooling 3V 2(PO 4) 3
Described lithium salts is a kind of in lithium acetate, lithium chloride, lithium nitrate and the lithium fluoride.
Described phosphate is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate and the sodium phosphate.
Described organic acid is a kind of in ascorbic acid, adipic acid, malonic acid and the citric acid
Described inert gas is a kind of in nitrogen and the argon gas.
The present invention directly uses the pentavalent vanadium to make raw material, has solved the easy problem of oxidation of vanadium ion; Reduced sintering temperature, can suppress too growing up of sample crystal grain effectively, made that institute's synthetic material particle size distribution is even, tiny, conductivity improves; Adjustable between synthesis temperature 400-700 ℃, can obtain varigrained material; Method is simple and convenient, be easy to control; The charge-discharge performance of sample and cycle performance improve, and have reduced cost.
Description of drawings
Fig. 1 is No. 3 sample Li of the embodiment of the invention 1 3V 2(PO 4) 3XRD figure.
Fig. 2 is No. 3 sample Li of the embodiment of the invention 1 3V 2(PO 4) 3SEM figure.
Fig. 3 is No. 3 sample Li of the embodiment of the invention 1 3V 2(PO 4) 3The first charge-discharge curve.
Fig. 4 is No. 3 sample Li of the embodiment of the invention 1 3V 2(PO 4) 3The cycle performance curve.
Embodiment
Embodiment 1:
The 0.095mol vanadium pentoxide powder is heated to 600 ℃; and constant temperature 4h makes to pour into rapidly in the container that water is housed after its melting and forms brown-red solution; in solution, add 0.31mol lithium acetate, 0.305mol diammonium hydrogen phosphate and 0.105mol ascorbic acid then; after mixing; under the protection of nitrogen, respectively at 400 ℃, 500 ℃, 600 ℃, 700 ℃ sintering 5h, be finished product Li after the cooling 3V 2(PO 4) 3Resulting product shows to be Li through X-ray diffraction analysis 3V 2(PO 4) 3, do not have any dephasign, can obtain the particle diameter of product by SEM about 0.5 μ m.With resulting product be assembled into the experiment button cell survey its charging and discharging capacity and cycle performance, under the multiplying power of 1C, discharge and recharge, its first discharge capacity and the circulation 30 times after discharge capacity see Table 1.
The experiment condition of table 1 embodiment 1 and result
Numbering Sintering temperature/℃ Sintering time/h Initial charge capacity/mAhg -1 Discharge capacity/mAhg first -1 The 30th discharge capacity/mAhg -1
1 400 5 115 97 80
2 500 5 130 122 113
3 600 5 135 129 124
4 700 5 129 119 109
Embodiment 2:
The 0.10mol vanadium pentoxide powder is heated to 900 ℃; and constant temperature 1h makes to pour into rapidly in the container that water is housed after the vanadic anhydride melting and forms brown-red solution; in solution, add 0.30mol lithium fluoride, 0.30mol ammonium dihydrogen phosphate (ADP) and 0.10mol adipic acid then; after mixing; under the protection of argon gas, in 600 ℃ of sintering 5,10,15 and 20h respectively, be finished product Li after the cooling 3V 2(PO 4) 3Resulting product shows to be Li through X-ray diffraction analysis 3V 2(PO 4) 3, do not have any dephasign, can obtain the particle diameter of product by SEM about 0.5 μ m.With resulting product be assembled into the experiment button cell survey its charging and discharging capacity and cycle performance, under the multiplying power of 1C, discharge and recharge, its first discharge capacity and the circulation 30 times after discharge capacity see Table 2.
The experiment condition of table 2 embodiment 2 and result
Numbering Sintering temperature/℃ Sintering time/h Initial charge capacity/mAhg -1 Discharge capacity/mAhg first -1 The 30th discharge capacity/mAhg -1
1 600 5 115 90 72
2 600 10 120 111 91
3 600 15 133 126 120
4 600 20 129 117 105
Embodiment 3:
The 0.105mol vanadium pentoxide powder is heated to 800 ℃; and constant temperature 2h makes to pour into rapidly in the container that water is housed after its melting and forms brown-red solution; in solution, add 0.305mol lithium chloride, 0.31mol potassium phosphate and 0.105mol malonic acid then; after mixing; under the protection of argon gas, in respectively at 450 ℃, 550 ℃, 650 ℃, 700 ℃ sintering 20h, be finished product Li after the cooling 3V 2(PO 4) 3Resulting product shows to be Li through X-ray diffraction analysis 3V 2(PO 4) 3, do not have any dephasign, can obtain the particle diameter of product by SEM about 0.5 μ m.With resulting product be assembled into the experiment button cell survey its charging and discharging capacity and cycle performance, under the multiplying power of 1C, discharge and recharge, its first discharge capacity and the circulation 30 times after discharge capacity see Table 3.
The experiment condition of table 3 embodiment 3 and result
Numbering Sintering temperature/℃ Sintering time/h Initial charge capacity/mAhg -1 Discharge capacity/mAhg first -1 The 30th discharge capacity/mAhg -1
1 450 20 108 93 73
2 550 20 128 110 99
3 650 20 132 123 115
4 700 20 116 99 74
Embodiment 4:
The 0.10mol vanadium pentoxide powder is heated to 700 ℃; and constant temperature 3h makes to pour into rapidly in the container that water is housed after its melting and forms brown-red solution; in solution, add 0.29mol lithium nitrate, 0.29mol sodium phosphate and 0.095mol citric acid then; after mixing; under the protection of nitrogen, in 550 ℃ of difference sintering 6,9,12,19h, be finished product Li after the cooling 3V 2(PO 4) 3Resulting product shows to be Li through X-ray diffraction analysis 3V 2(PO 4) 3, do not have any dephasign, can obtain the particle diameter of product by SEM about 0.5 μ m.With resulting product be assembled into the experiment button cell survey its charging and discharging capacity and cycle performance, under the multiplying power of 1C, discharge and recharge, its first discharge capacity and the circulation 30 times after discharge capacity see Table 4.
The experiment condition of table 4 embodiment 4 and result
Numbering Sintering temperature/℃ Sintering time/h Initial charge capacity/mAhg -1 Discharge capacity/mAhg first -1 The 30th specific discharge capacity/mAhg -1
1 550 6 125 110 95
2 550 9 120 106 97
3 550 12 130 121 109
4 550 19 119 104 88

Claims (1)

1. a sol-gel process prepares the method for cathode material lithium vanadium phosphate of lithium ion battery, it is characterized in that concrete steps are:
(1) vanadium pentoxide powder is heated to 600-900 ℃, and constant temperature 1-4h makes to pour into rapidly in the container that water is housed after its melting and form brown-red solution, this solution left standstill 4-16h can form V 2O 5NH 2The O wet gel; With removing most of moisture after the wet gel washing, then at 70-100 ℃ of lower vacuum drying 4-16h, grind and obtain the pentoxide gel powder;
(2) the above-mentioned pentoxide gel powder for preparing and lithium salts, phosphate, organic acid are 0.95-1.05: 2.9-3.1: 2.9-3.1 in molar ratio: after 0.95-1.05 mixes; under the protection of inert gas, in 400 ℃ of-700 ℃ of sintering 5-20h, be finished product Li after the cooling 3V 2(PO 4) 3
Described lithium salts is a kind of in lithium acetate, lithium chloride, lithium nitrate and the lithium fluoride;
Described phosphate is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, potassium phosphate and the sodium phosphate;
Described organic acid is a kind of in ascorbic acid, adipic acid, malonic acid and the citric acid;
Described inert gas is a kind of in nitrogen and the argon gas.
CNA2008100736791A 2008-07-14 2008-07-14 Method for producing lithium ion battery anode material vanadium lithium phosphate by sol-gel method Pending CN101315979A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102386413A (en) * 2011-11-11 2012-03-21 东莞市迈科科技有限公司 Method for preparing monoclinic lithium vanadium phosphate
CN102627266A (en) * 2012-04-20 2012-08-08 重庆市科学技术研究院 Vanadium titanium lithium phosphate material for positive electrode of lithium ion battery
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

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102386413A (en) * 2011-11-11 2012-03-21 东莞市迈科科技有限公司 Method for preparing monoclinic lithium vanadium phosphate
CN102386413B (en) * 2011-11-11 2013-12-04 东莞市迈科科技有限公司 Method for preparing monoclinic lithium vanadium phosphate
CN102627266A (en) * 2012-04-20 2012-08-08 重庆市科学技术研究院 Vanadium titanium lithium phosphate material for positive electrode of lithium ion battery
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

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Open date: 20081203