CN101101986A - Making method of anode material Li3V2(PO4)3 of high performance/price ration lithium ion battery - Google Patents

Making method of anode material Li3V2(PO4)3 of high performance/price ration lithium ion battery Download PDF

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Publication number
CN101101986A
CN101101986A CNA2007100528949A CN200710052894A CN101101986A CN 101101986 A CN101101986 A CN 101101986A CN A2007100528949 A CNA2007100528949 A CN A2007100528949A CN 200710052894 A CN200710052894 A CN 200710052894A CN 101101986 A CN101101986 A CN 101101986A
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lithium
anode material
citric acid
li3v2
ion batteries
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朱先军
罗卫城
董贤昌
董学斌
刘云霞
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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 is concerned with a kind of preparation method of anode material Li3V2(PO4)3 to lithium ion cell with sol-gel and carbothermal reduction; combine technology. It takes lithium hydroxide or lithium carbonate, ammonium vanadate and phosphoric acid as raw material, citric acid as complexing agent with 3 to 3.05 :2 Li/V mol ratio and 2 to 4 : 3 to 3.05 citric acid/ Li mol ratio. Put into water to get sol, vaporize the solvent to get gel, dry to get disaggrega-tire organic matter in advance in 300 to 400 degree air, then bake for 8 to 16 hours in Ar or N2 atmosphere containing H24-8 percent during 700 to 900 degree, cool and grind to get Li3V2(PO4)3/C. This anode material has 132 mAh/g specific votume and 3.6 to 4.15 V work pressure with the range of 3 to 4.2 V pressure. Compared with LiCoO2, Li3V2(PO4)3 is advanced ion cell with high capability anode.

Description

High performance/price ration lithium ion battery positive electrode Li 3V 2(PO 4) 3The preparation method
Technical field
The present invention relates to a kind of high performance/price ration lithium ion battery positive electrode Li 3V 2(PO 4) 3The preparation method.Belong to electrochemistry and electronics applications technical field.
Background technology
Lithium ion battery is present state-of-the-art high specific energy chemical power source, is widely used in fields such as mobile communication, computer, video camera, camera, portable instrument, also can be used as the supporting power supply of electric automobile first-selection.Wherein, the preparation of positive electrode is one of technology of lithium ion battery development and manufacture process key, thus people dropped into a large amount of man power and materials study have the specific capacity height, current potential height, low, the free of contamination positive electrode of price.Studying maximum is LiCoO 2, LiNiO 2, LiMn 2O 4, LiNi xMnt yCo 1-x-yO 2And LiFePO 4That commercial is the most ripe is LiCoO 2, but the Co resource-constrained costs an arm and a leg, and poisonous, so its application has been subjected to certain restriction.At present, the polyanionic compound Li that has olivine structural 3M 2(PO 4) 3Receive much attention.Wherein, the Li that has monocline 3V 2(PO 4) 3Be considered to the most promising anode material for lithium-ion batteries, Stability Analysis of Structures in this material charge and discharge process, and have good cyclical stability and heat endurance.Take off two lithium ions of embedding before at 4.2V voltage (with respect to lithium metal), theoretical specific capacity is 133mAh/g; Took off three lithium ions of embedding before 4.8V voltage, theoretical specific capacity is 197mAh/g, is considered to the highest positive electrode of specific capacity in the phosphate structural compounds, thereby becomes one of focus of current anode material for lithium-ion batteries research.[Chem.Mater., 14 (2002) 4684-4693.] such as D Morgan use H 2Reducing process, [J.Electrochem.Soc., 150 (2003) A684-A688.] the reduction with carbon methods such as J Barker are synthesized Li 3V 2(PO 4) 3, but because their synthetic being difficult to grasped, still be at present the laboratory research stage.
Summary of the invention
The object of the present invention is to provide a kind of anode material for lithium-ion batteries Li for preparing 3V 2(PO 4) 3New method.This method, reduces production costs when guaranteeing synthetic material high performance technology index from raw material cheap and easy to get; selected simple for process; the technology path that is fit to large-scale production has guaranteed stability, feasibility and the uniformity of product quality.
The object of the present invention is achieved like this:
A kind of anode material for lithium-ion batteries Li 3V 2(PO 4) 3The preparation method.It is characterized in that the method that adopts sol-gel to combine with carbon reduction, with lithium hydroxide or lithium carbonate, ammonium metavanadate and phosphoric acid are raw material, citric acid is complexing agent, is 3.00～3.05: 2 by the mol ratio of Li/V, and citric acid/Li mol ratio is 2～4: 3～3.05 scopes, accurate each raw material of weighing, the colloidal sol of making soluble in water is regulated pH as 9 take ammoniacal liquor, constant temperature in 80 ℃ of water-baths, evaporating solvent, gel, drying, with gel after the drying at 300～400 ℃ of temperature predecomposition organic matter in air; Again mixture is placed the high-temperature atmosphere sintering furnace, containing H 2Ar or N 2Mixed atmosphere in, 700～900 ℃ of roastings 8～16 hours are taken out after the cooling, ball milling namely gets anode material for lithium-ion batteries Li 3V 2(PO 4) 3/ C.
Wherein, the said H that contains 2Ar or N 2Mixed atmosphere for containing H 24～8% Ar or N 2
After tested, the anode material for lithium-ion batteries Li that makes 3V 2(PO 4) 3The carbon containing quality of/C is 6～15%, and being evenly distributed of carbon, and has effectively improved Li 3V 2(PO 4) 3The electric conductivity of material; Chemical property is good, and discharge potential is (with respect to the lithium reference electrode) between 3.6～4.15V, can be used as anode material for lithium-ion batteries.
Compared with the prior art, the Li of the present invention's preparation 3V 2(PO 4) 3/ C positive electrode has following outstanding feature:
1, owing to adopt sol-gel process, raw material reaches molecular level combination, good mixing effect.Citric acid not only plays the complexing agent effect, and at H 2/ Ar or N 2Resolve into carbon in the mixed atmosphere, played the effect of reducing agent, make V 5+→ V 3+, excessive carbon is evenly distributed on product Li 3V 2(PO 4) 3In, improved its conductivity effectively.
2, the Li of preparation 3V 2(PO 4) 3Material electrochemical performance is good, has monocline, the 0.2C multiplying power discharging, and in 3～4.2V voltage range, specific capacity reaches 132mAh/g, and discharge potential is (with respect to the lithium reference electrode) between 3.6～4.15V, and has good cyclical stability.With LiCoO 2Compare Li 3V 2(PO 4) 3It is the positive electrode that advanced lithium ion battery has high performance-price ratio.
3, technology is simple, is easy to grasp, and realizes easily industrial-scale production.
Description of drawings
Fig. 1 is the Li that the present invention prepares 3V 2(PO 4) 3Add an amount of additive and binding agent and make the first charge-discharge curve of electrode.
Embodiment
The invention will be further described below in conjunction with example.
Embodiment 1:
Accurately take by weighing LiOH.H 2O 4.196 grams, NH 4VO 37.799 gram, (mol ratio of Li/V is 3.00: 2) gets H 3PO 46.287 milliliter, citric acid 14.009 grams (citric acid/Li mol ratio is 2: 3.00); Citric acid is dissolved in 400 ml waters, under constantly stirring, adds NH 4VO 3, add LiOH.H again 2O drips H then 3PO 4, regulating the pH value with ammoniacal liquor is 9, makes colloidal sol, and colloidal sol is placed 80 ℃ of waters bath with thermostatic control, constantly stirs, evaporation moisture content gets gel; 100 ℃ of dryings 10 hours, at 300 ℃, predecomposition is 3 hours in the air with desiccant gel; Grind, mixture is placed high temperature sintering furnace, at 8%H 2In the mixed atmosphere of+Ar, 800 ℃ of roastings 8 hours are cooled to room temperature, and ball milling is crossed 300 mesh sieves, promptly gets Li 3V 2(PO 4) 3Product; After tested, the product phosphorus content is 6%.Package spare.
Embodiment 2:
Accurately take by weighing LiOH.H 2The O4.266 gram, NH 4VO 37.799 gram (mol ratio of Li/V is 3.05: 2) is got H 3PO 46.287 milliliter, citric acid 28.018 grams (citric acid/Li mol ratio is 4: 3.05); Citric acid is dissolved in 400 ml waters, under constantly stirring, adds NH 4VO 3, add again LiOH.H 2O drips H then 3PO 4, regulating the pH value with ammoniacal liquor is 9, makes colloidal sol, and colloidal sol is placed 80 ℃ of waters bath with thermostatic control, constantly stirs, evaporation moisture content gets gel; 100 ℃ of dryings 10 hours, at 300 ℃, predecomposition is 3 hours in the air with desiccant gel; Grind, mixture is placed high temperature sintering furnace, at 8%H 2In the mixed atmosphere of+Ar, 700 ℃ of roastings 16 hours are cooled to room temperature, and ball milling is crossed 300 mesh sieves, namely gets Li 3V 2(PO 4) 3Product; After tested, the product phosphorus content is 15%.Package spare.
Embodiment 3:
Accurately take by weighing Li 2CO 33.756 gram, NH 4VO 37.799 gram (please the mol ratio by Li/V is 3.00: 2) is got H 3PO 46.287 milliliter, citric acid 28.018 grams (citric acid/Li mol ratio is 4: 3); Citric acid is dissolved in 400 ml waters, under constantly stirring, adds NH 4VO 3, add LiOH.H again 2O drips H then 3PO 4, regulating the pH value with ammoniacal liquor is 9, makes colloidal sol, and colloidal sol is placed 80 ℃ of waters bath with thermostatic control, constantly stirs, evaporation moisture content gets gel; 100 ℃ of dryings 10 hours, at 400 ℃, predecomposition is 3 hours in the air with desiccant gel; Grind, mixture is placed high temperature sintering furnace, at 8%H 2In the mixed atmosphere of+Ar, 900 ℃ of roastings 8 hours are cooled to room temperature, and ball milling is crossed 300 mesh sieves, promptly gets Li 3V 2(PO 4) 3Product; After tested, the product phosphorus content is 14%.Package spare.

Claims (3)

1, a kind of anode material for lithium-ion batteries Li 3V 2(PO 4) 3The preparation method.It is characterized in that, the method that adopts sol-gel to combine with carbon reduction, with lithium hydroxide or lithium carbonate, ammonium metavanadate and phosphoric acid are raw material, and citric acid is complexing agent, are 3.00～3.05: 2 by the mol ratio of Li/V, citric acid/Li mol ratio is 2～4: 3～3.05 colloidal sol, the gels made soluble in water, predecomposition organic matter in 300～400 ℃ of temperature air too 700～900 ℃ of temperature, is containing H again 2Ar or N 2Mixed atmosphere in roasting 8～16 hours, take out after the cooling, ball milling namely gets anode material for lithium-ion batteries Li 3V 2(PO 4) 3/ C.
2, by the said anode material for lithium-ion batteries Li of claim 1 3V 2(PO 4) 3The preparation method, it is characterized in that prepared anode material for lithium-ion batteries Li 3V 2(PO 4) 3The carbon containing quality is 6～15% among the/C.
3, by the said anode material for lithium-ion batteries Li of claim 1 3V 2(PO 4) 3The preparation method, it is characterized in that the said H of containing 2Ar or N 2Mixed atmosphere for containing H 24～8% Ar or N 2
CNA2007100528949A 2007-08-06 2007-08-06 Making method of anode material Li3V2(PO4)3 of high performance/price ration lithium ion battery Pending CN101101986A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101841038A (en) * 2009-03-16 2010-09-22 Tdk株式会社 The manufacture method of active material, active material, electrode and lithium rechargeable battery
CN101630731B (en) * 2009-07-27 2011-03-30 深圳市德方纳米科技有限公司 Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof
CN101630730B (en) * 2009-07-27 2011-03-30 深圳市德方纳米科技有限公司 Nanoscale lithium iron phosphate compound and preparation method thereof
CN102088081A (en) * 2011-01-17 2011-06-08 浙江大学 Preparation method of anode material of lithium-ion power battery lithium vanadium phosphate
CN101734637B (en) * 2008-11-20 2011-08-31 中国科学院理化技术研究所 Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery
CN102386412A (en) * 2011-11-11 2012-03-21 中南大学 Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof
CN102723489A (en) * 2012-06-27 2012-10-10 北京化工大学 Nitrogen-doped carbon-coated Li3V2(PO4)3 cathode material and preparation method thereof
CN102020468B (en) * 2009-09-18 2012-12-26 中国电子科技集团公司第十八研究所 A process for synthesizing Li3V2(PO4)3/C composite material using one step carbothermic reduction method
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
CN112186168A (en) * 2020-10-10 2021-01-05 宁波大学 Zinc ion battery electrode material and preparation method and application thereof

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101734637B (en) * 2008-11-20 2011-08-31 中国科学院理化技术研究所 Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery
CN101841038A (en) * 2009-03-16 2010-09-22 Tdk株式会社 The manufacture method of active material, active material, electrode and lithium rechargeable battery
US8445135B2 (en) 2009-03-16 2013-05-21 Tdk Corporation Method of manufacturing active material, active material, electrode, and lithium-ion secondary battery
CN101630731B (en) * 2009-07-27 2011-03-30 深圳市德方纳米科技有限公司 Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof
CN101630730B (en) * 2009-07-27 2011-03-30 深圳市德方纳米科技有限公司 Nanoscale lithium iron phosphate compound and preparation method thereof
CN102020468B (en) * 2009-09-18 2012-12-26 中国电子科技集团公司第十八研究所 A process for synthesizing Li3V2(PO4)3/C composite material using one step carbothermic reduction method
CN102088081A (en) * 2011-01-17 2011-06-08 浙江大学 Preparation method of anode material of lithium-ion power battery lithium vanadium phosphate
CN102088081B (en) * 2011-01-17 2013-01-09 浙江大学 Preparation method of anode material of lithium-ion power battery lithium vanadium phosphate
CN102386412A (en) * 2011-11-11 2012-03-21 中南大学 Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof
CN102723489A (en) * 2012-06-27 2012-10-10 北京化工大学 Nitrogen-doped carbon-coated Li3V2(PO4)3 cathode material and preparation method thereof
CN102723489B (en) * 2012-06-27 2014-04-02 北京化工大学 Nitrogen-doped carbon-coated Li3V2(PO4)3 cathode material and preparation method thereof
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
CN112186168A (en) * 2020-10-10 2021-01-05 宁波大学 Zinc ion battery electrode material and preparation method and application thereof
CN112186168B (en) * 2020-10-10 2021-10-19 宁波大学 Zinc ion battery electrode material and preparation method and application thereof

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