CN100503451C - Positive electrode material Li(1+X)V3O8 of Li-ion battery preparing process - Google Patents

Positive electrode material Li(1+X)V3O8 of Li-ion battery preparing process Download PDF

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CN100503451C
CN100503451C CNB2007100176278A CN200710017627A CN100503451C CN 100503451 C CN100503451 C CN 100503451C CN B2007100176278 A CNB2007100176278 A CN B2007100176278A CN 200710017627 A CN200710017627 A CN 200710017627A CN 100503451 C CN100503451 C CN 100503451C
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lithium
preparation
ion batteries
anode material
citric acid
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CN101054204A (en
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周园
岳鸿飞
李宁
张昕岳
邓小宇
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to the preparation method for Li1+xV3O8 as cathode material for lithium ion battery, which comprises the steps of that: (1)the lithium raw material, the vanadium raw material and the ethylenediaminetetraacetic acid or/and citric acid are put into a reaction kettle in a proportion of 1:2.25:3~1:3.75:5, and then distilled water which is 10~25 times of the total of the mixture is added therein, and then the mixture is heated at 50~90 DEG C, agitated and dissolved to obtain the uniform and clear solution or suspending solution; (2)the solution is further heated and agitated until the surface moisture is dried so as to obtain the jello which forms the fluffy and porous precursor by means of vacuum drying; (3)the precursor is grinded uniformly in a mortar, and then the synthesis reaction is executed at 200~700 DEG C for 2~10 hours; finally, the powder of Li1+xV3O8 as cathode material for lithium ion battery is obtained after cooling, milling and screening. In the simulation battery circulation performance testing, the Li1+xV3O8 of the present invention have higher initial circulation capacity which is stable after a plurality of circulations, and has excellent charging/discharging performance.

Description

A kind of anode material for lithium-ion batteries Li 1+xV 3O 8The preparation method
Technical field
The invention belongs to chemical field, relate to a kind of preparation of anode material for lithium-ion batteries, relate in particular to a kind of lamellar compound Li 1+xV 3O 8The preparation method of anode material for lithium-ion batteries.
Background technology
Earlier 1990s is dropped into the commercial Li-Ion rechargeable battery that uses, and can fill energy storage battery as a kind of green, efficient, portable, has following plurality of advantages: 1, energy density height; 2, average output voltage height is Ni-Cd, Ni-MH battery 3 times; 3, output rating is big; 4, self-discharge is little, and every month below 10%, less than half of Ni-Cd, Ni-MH battery; 5, memory-less effect, cycle performance is superior; But 6 fast charging and dischargings; 7, efficiency for charge-discharge height; 8, operating temperature range is wide, and working temperature is about-25-45 ℃; 9 non-environmental-pollutions are green battery; 10 long service life, thus in minicell, maintain the leading position.Li-Ion rechargeable battery is as the power supply of mobile telephone and other mancarried electronic aids at present, and the occuping market is leading, the demand sharp increase.Lithium ion battery mainly comprises positive pole, negative pole and ionogen, and the lithium ion battery excellent properties depends on positive and negative electrode material, ionogen and membranous selection and preparation to a great extent.The focus of positive electrode current investigation of materials mainly concentrates on stratiform Li xMO 2With spinel type Li xM 2O 4On the compound of structure (M=Co, Ni, Mn, a series of transition metal ions of V grade in an imperial examination).Because world's cobalt resource is very limited, causes Li xCoO 2The material price costliness; The Li that composite structure is complete xNiO 2Comparatively difficult; Li xMn 2O 4In use capacity attenuation is fast.And lamellar compound Li 1+xV 3O 8Have good embedding lithium ability (the per molecule unit can reach 4.5 lithium atoms at most), have simultaneously cheap, be easy to synthesize, advantage such as specific storage height, average voltage height, charge-discharge velocity are fast, have extended cycle life, also receive much attention.And China's navajoite resource is more, total retained reserve V 2O 52,596 ten thousand tons, occupy the 3rd in the world, be easy to get factors such as with low cost and comprehensive electrochemical properties, lamellar compound Li if consider raw material 1+xV 3O 8Be suitable for scale operation and application.
Summary of the invention
The purpose of this invention is to provide a kind of lamellar compound Li that good embedding lithium ability, specific storage height, average voltage height, charge-discharge velocity are fast, have extended cycle life, be easy to advantages such as synthesizing, cheap that has 1+xV 3O 8The preparation method of anode material for lithium-ion batteries.
The present invention prepares anode material for lithium-ion batteries Li 1+xV 3O 8Method, comprise the steps: successively
1. with lithium raw material, vanadium raw materials and ethylenediamine tetraacetic acid (EDTA) or/and citric acid is the ratio of 1:2.25:3～1:3.75:5 with the mol ratio joins in the reactor, again to the distilled water of 10～25 times of the amount total amounts that wherein adds lithium raw material, vanadium raw materials and ethylenediamine tetraacetic acid (EDTA) compounding substances, be heated to 50～90 ℃, stir, dissolving obtains homogeneous transparent solution or suspension liquid;
2. continue heating and stirring, obtain jello until the evaporate to dryness surface-moisture, and jello vacuum-drying is made the bulk multi-hole presoma;
3. gained bulk multi-hole presoma is ground in mortar evenly, again 200～700 ℃ of following building-up reactionss 2～10 hours; Cooling, grinding is sieved, and obtains powder anode material for lithium-ion batteries Li 1+xV 3O 8
Described step 1. in, when adding citric acid, earlier the citric acid water being mixed with concentration is 1.0～6.0molL -1Solution, under whipped state, slowly join in the reactor again.
Described step 1. in, when adding lithium raw material, vanadium raw materials, ethylenediamine tetraacetic acid (EDTA) and citric acid simultaneously, its mol ratio is 1:2.25:2:1～1:3.75:3:2.
Described lithium raw material is at least a in analytical pure Lithium Citrate de, Lithium Acetate, Quilonum Retard or the lithium nitrate.
Described vanadium raw materials is ammonium meta-vanadate or Vanadium Pentoxide in FLAKES.
The 2. middle vacuum drying vacuum tightness of jello of described step is 10～10 4Pa, drying temperature are 80～140 ℃.
The building-up reactions of described step in 3. is to finish in stoving oven; The described furnace cooling that is cooled to, speed of cooling are 10～50 ℃ of h -1
The anode material for lithium-ion batteries Li of the present invention's preparation 1+xV 3O 8, to measure through X ray diffracting spectrum, its diffraction peak is clear and sharp-pointed, and is corresponding fully with standard card, illustrates that the product of the present invention's preparation is Li 1+xV 3O 8Lamellar compound, and complete in crystal formation.
The anode material for lithium-ion batteries of the present invention preparation, through aas determination lithium content wherein, oxidation reduction titration is measured wherein content of vanadium, determines that its chemical formula is Li 1+xV 3O 8, 0.2 ≦ x ≦ 1.3 wherein.
The synthetic material Li of the present invention's preparation 1+xV 3O 8Through the test of simulated battery cycle performance, the initial cycle capacity is greater than 200mAh/g, and after repeatedly circulating, circulation volume is relatively stable, illustrates to have higher initial capacity and favorable charge-discharge cycle performance.
The anode material for lithium-ion batteries Li of the present invention's preparation 1+xV 3O 8Have following advantage compared to existing technology:
1, liquid-phase mixing technology is adopted in preparation of the present invention, at ion, molecular scale diffusive mixing, has effectively guaranteed the mixing of material, the degree that is uniformly dispersed, and has effectively reduced synthesis reaction temperature, reduces the reaction times, significantly reduces energy consumption;
2, the present invention with ethylenediamine tetraacetic acid (EDTA) or/and citric acid as the synthetic jelly of sequestrant, make and realized that all lithium and vanadium are with the mixed uniformly effect of atom level on microtexture and the macrostructure, formed homogeneous solution of the same name at aqueous phase, make the positive electrode material composition of preparation be easy to control, powder is even, purity is high, process degree of controllability height.
2, preparation process of the present invention is simple, and raw material cheaply is easy to get, and preparation cost is low, and building-up process toxicological harmless deposits yields meets the environmental protection notion.
3, the synthetic materials Li of the present invention's preparation 1+xV 3O 8Be lamellar compound, its complete in crystal formation, the product purity height has good embedding lithium ability (the per molecule unit can reach 4.5 lithium atoms at most), and electrochemistry is good: specific storage height, average voltage height, charge-discharge velocity be fast, have extended cycle life.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the synthetic materials of the embodiment of the invention 1 preparation
Fig. 2 is the simulated battery cycle performance test result of the synthetic material of the embodiment of the invention 1 preparation
Fig. 3 is the X ray diffracting spectrum of the synthetic materials of the embodiment of the invention 2 preparations
Fig. 4 is the simulated battery cycle performance test result of the synthetic material of the embodiment of the invention 2 preparations
Fig. 5 is the X ray diffracting spectrum of the synthetic materials of the embodiment of the invention 3 preparations
Fig. 6 is the simulated battery cycle performance test result of the synthetic material of the embodiment of the invention 3 preparations
Embodiment
Embodiment 1: Lithium Citrate de, ammonium meta-vanadate, EDTA and the citric acid mol ratio with 1:2.25:3:1 is taken by weighing; Earlier lemon acid lithium, ammonium meta-vanadate, EDTA are put into reactor, again to the distilled water that wherein adds 20 times of Quilonum Retard, ammonium meta-vanadate and EDTA amount of substance total amounts, be heated to 50 ℃ of also magnetic agitation, dissolvings, solution becomes orange earlier, finally becomes the mazarine clear solution; It is 2.5molL that the citric acid that takes by weighing is mixed with concentration -1The aqueous solution, under whipped state, slowly be added dropwise in the mazarine clear solution, process is emitted with bubble, treats that citric acid drips, and continue to stir 1h, 80 ℃ of evaporating water, is 10 in vacuum tightness then 4Pa, temperature is that 110 ℃ of following vacuum-dryings must be the pewter solid precursor in 4 hours, is placed in the mortar to grind evenly, puts into stoving oven, at 550 ℃ of sintering Synthetic 2s 0 hour, furnace cooling, grinding sieves promptly gets Li 1+xV 3O 8Positive electrode material, material X-ray diffraction result such as accompanying drawing 1.Adopt the synthetic Li of present embodiment 1+xV 3O 8Material is a positive electrode active materials, and acetylene black is conductive agent, and PVDF makees binding agent, and three's mass ratio is that 87: 8: 5 compositions are anodal, and bright lithium sheet is a negative pole, 1molL -1Concentration LiPF 6EC+EMC (volume ratio 1:1) solution be electric drain, Celgard 2400 is a barrier film, in German Unilab glove box, assemble simulated battery, utilize the LAND CT2001A of Wuhan Jin Nuo Electronics Co., Ltd. type battery performance comprehensive tester to carry out the test cell performance test, simulated battery cycle performance test result such as accompanying drawing 2.
Embodiment 2: Lithium Citrate de, ammonium meta-vanadate and EDTA are taken by weighing with the mol ratio of 1:3:3, put into reactor, again to the distilled water that wherein adds 20 times of Quilonum Retard, ammonium meta-vanadate and EDTA amount of substance total amounts, be heated to 60 ℃ of also magnetic agitation, dissolvings, solution becomes orange earlier, finally becomes the mazarine clear solution, continues to stir 1h again, 70 ℃ of evaporating water, be 10 in vacuum tightness then 2Pa, temperature is that 120 ℃ of following vacuum-dryings must be the pewter solid precursor in 4 hours, is placed in the mortar to grind evenly, puts into stoving oven, at 630 ℃ of sintering Synthetic 2s 0 hour, furnace cooling, grinding sieves promptly gets Li 1+xV 3O 8Positive electrode material, material X-ray diffraction result such as Fig. 3.Adopt the synthetic Li of present embodiment 1+xV 3O 8Material is a positive electrode active materials, and acetylene black is conductive agent, and PVDF makees binding agent, and three's mass ratio is that 87:8:5 forms positive pole, and bright lithium sheet is a negative pole, 1molL -1Concentration LiPF 6EC+EMC (volume ratio 1:1) solution be electric drain, Celgard 2400 is a barrier film, in German Unilab glove box, assemble simulated battery, utilize the LAND CT2001A of Wuhan Jin Nuo Electronics Co., Ltd. type battery performance comprehensive tester to carry out the test cell performance test, simulated battery cycle performance test result such as accompanying drawing 4.
Embodiment 3: with Lithium Citrate de, ammonium meta-vanadate and citric acid is that the ratio of 1:3.75:4 takes by weighing with the mol ratio; Earlier Quilonum Retard and ammonium meta-vanadate are put into reactor,, under magnetic stirring apparatus, be heated to 70 ℃ and stirring, make it become even faint yellow suspension liquid again to the distilled water that wherein adds 10 times of Quilonum Retard and ammonium meta-vanadate amount of substance total amounts; It is 5.0molL that the citric acid water is mixed with concentration -1Solution, under whipped state, slowly splash in the solution of reactor, solution colour becomes orange earlier, finally becomes mazarine, and emitting with bubble; 85 ℃ of evaporating water, be 10 in vacuum tightness then 3Pa, temperature is 130 ℃ of following vacuum-dryings 4 hours, obtains the black-and-blue solid precursor of bulk multi-hole; Then the black solid presoma is placed mortar to grind evenly, put into stoving oven, synthesized 15 hours at 600 ℃ of sintering, furnace cooling grinds evenly, and grinding sieves promptly gets Li 1+xV 3O 8Positive electrode material, material X-ray diffraction result such as Fig. 5.Adopt the synthetic Li of present embodiment 1+xV 3O 8Material is a positive electrode active materials, and acetylene black is conductive agent, and PVDF makees binding agent, and three's mass ratio is that 87:8:5 forms positive pole, and bright lithium sheet is a negative pole, 1molL -1Concentration LiPF 6EC+EMC (volume ratio 1:1) solution be electric drain, Celgard 2400 is a barrier film, in German Unilab glove box, assemble simulated battery, utilize the Wuhan LANDCT2001A of Jin Nuo Electronics Co., Ltd. type battery performance comprehensive tester to carry out the test cell performance test, simulated battery cycle performance test result such as Fig. 6.

Claims (7)

1, a kind of anode material for lithium-ion batteries Li 1+xV 3O 8The preparation method, comprise the steps: successively
1. with lithium raw material, vanadium raw materials and ethylenediamine tetraacetic acid (EDTA) or/and citric acid is the ratio of 1:2.25:3～1:3.75:5 with the mol ratio joins in the reactor, again to the distilled water of 10～25 times of the amount total amounts that wherein adds compounding substances, be heated to 50～90 ℃, stir, dissolving obtains homogeneous transparent solution or suspension liquid;
2. continue heating and stirring, obtain jello until the evaporate to dryness surface-moisture, and jello vacuum-drying is made the bulk multi-hole presoma;
3. gained bulk multi-hole presoma is ground in mortar evenly, again 200～700 ℃ of following building-up reactionss 2～10 hours; Cooling, grinding is sieved, and obtains powder anode material for lithium-ion batteries Li 1+xV 3O 8Wherein ,-0.2 ≦ x ≦ 1.3.
2, anode material for lithium-ion batteries Li according to claim 1 1+xV 3O 8The preparation method, it is characterized in that: described step 1. in, when adding citric acid, earlier the citric acid water being mixed with concentration is 1.0～6.0molL -1Solution, under whipped state, slowly join in the reactor again.
3, anode material for lithium-ion batteries Li according to claim 1 1+xV 3O 8The preparation method, it is characterized in that: described step 1. in, when adding lithium raw material, vanadium raw materials, ethylenediamine tetraacetic acid (EDTA) and citric acid simultaneously, its mol ratio is 1:2.25:2:1～1:3.75:3:2.
4, as anode material for lithium-ion batteries Li as described in the claim 1,2 or 3 1+xV 3O 8The preparation method, it is characterized in that: described lithium raw material is at least a in analytical pure Lithium Citrate de, Lithium Acetate, Quilonum Retard or the lithium nitrate.
5, as anode material for lithium-ion batteries Li as described in the claim 1,2 or 3 1+xV 3O 8The preparation method, it is characterized in that: described vanadium raw materials is ammonium meta-vanadate or Vanadium Pentoxide in FLAKES.
6, as anode material for lithium-ion batteries Li as described in the claim 1,2 or 3 1+xV 3O 8The preparation method, it is characterized in that: described step 2. in the vacuum drying vacuum tightness of jello be 10～10 4Pa, drying temperature are 80～140 ℃.
7, as anode material for lithium-ion batteries Li as described in the claim 1,2 or 3 1+xV 3O 8The preparation method, it is characterized in that: the building-up reactions of described step in 3. is to finish in stoving oven; The described furnace cooling that is cooled to, speed of cooling are 10～50 ℃ of h -1
CNB2007100176278A 2007-03-30 2007-03-30 Positive electrode material Li(1+X)V3O8 of Li-ion battery preparing process Expired - Fee Related CN100503451C (en)

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CN102386386A (en) * 2011-11-11 2012-03-21 中南大学 Preparation method for cathode material lithium vanadium oxide of lithium battery
CN102531057B (en) * 2012-01-17 2013-10-30 重庆市科学技术研究院 Method for preparing lithium vanadate as cathode material of lithium ion battery
CN102891313A (en) * 2012-10-17 2013-01-23 中南大学 Method for preparing vanadate anode material
CN103413945A (en) * 2013-08-27 2013-11-27 昆明理工大学 Manufacturing method of positive material for lithium ion battery
CN105118963B (en) * 2015-07-21 2018-03-02 广东省新材料研究所 A kind of transparent positive electrode of lithium ion battery and preparation method thereof
CN109553133A (en) * 2018-10-23 2019-04-02 开封大学 It is a kind of to prepare lithium battery anode material lithium barium oxide LiV3O8Method
CN109704404A (en) * 2019-01-02 2019-05-03 成都先进金属材料产业技术研究院有限公司 The method that solution combustion prepares lithium vanadate
CN110773112A (en) * 2019-09-25 2020-02-11 中国科学院青海盐湖研究所 Modified manganese-based lithium ion sieve and preparation method thereof
CN114361431A (en) * 2021-08-20 2022-04-15 山东瑞福锂业有限公司 Process and method for regulating and controlling structure of regular micron sheet lithium carbonate material for ternary positive electrode material in lithium ion battery
CN113603139A (en) * 2021-08-24 2021-11-05 攀枝花学院 LiVO3Electrode material and rapid preparation method thereof

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CN1560936A (en) * 2004-02-16 2005-01-05 厦门大学 Preparing method of lithium manganese oxide and its application in battery

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CN1560936A (en) * 2004-02-16 2005-01-05 厦门大学 Preparing method of lithium manganese oxide and its application in battery

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