CN1964106A - A method to manufacture anode material of LiFePO4/C for lithium ion cell - Google Patents

A method to manufacture anode material of LiFePO4/C for lithium ion cell Download PDF

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CN1964106A
CN1964106A CNA2006101251248A CN200610125124A CN1964106A CN 1964106 A CN1964106 A CN 1964106A CN A2006101251248 A CNA2006101251248 A CN A2006101251248A CN 200610125124 A CN200610125124 A CN 200610125124A CN 1964106 A CN1964106 A CN 1964106A
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sintering
anode material
preparation
liohh
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CN100420074C (en
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张克立
王丽娜
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Zhejiang Zhenhua New Energy Co., Ltd.
Wuhan University WHU
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Wuhan University WHU
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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 related preparation method for LiFePO4/C as anode material of Li-ion cell comprises: selecting LiOH .H2O (or Li2CO3, CH3COOLi .2H2O), FePO4 .4H2O and PEG as material to mix evenly and make into rheologic state by adding water; with inert gas protection, sintering into the final material. This invention reduces cost, improves reaction efficiency, and fit to industrial production.

Description

A kind of anode material for lithium-ion batteries LiFePO 4The preparation method of/C
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, especially LiFePO 4The preparation method of/C cell positive material.
Background technology
Preparation LiFePO 4The method of/C cell positive material mainly is high temperature solid-state method and some solwution methods, as hydro thermal method, and coprecipitation or the like.The shortcoming one of these methods is that preparation process is loaded down with trivial details, is not suitable for suitability for industrialized production; The 2nd, these methods use expensive ferrous iron as source of iron more, have not only increased preparation cost, and the very easily oxidation of ferrous iron ingress of air, have improved the difficulty of control reaction condition, have reduced purity, performance and the production efficiency of product.
Summary of the invention
Problem to be solved by this invention provides a kind of anode material for lithium-ion batteries LiFePO 4The method of/C, this procedure is simple, and raw materials used is cheap, and products therefrom functional is convenient to suitability for industrialized production.
Technical scheme provided by the invention is: a kind of anode material for lithium-ion batteries LiFePO 4The method of/C is with FePO 44H 2O and LiOHH 2O, Li 2CO 3Or CH 3COOLi2H 2O and solid polyethylene glycol mix, and add entry furnishing rheology attitude, and sintering obtains anode material for lithium-ion batteries LiFePO under inert atmosphere then 4/ C.
Above-mentioned FePO 44H 2O and LiOHH 2O, Li 2CO 3Or CH 3COOLi2H 2The consumption mol ratio of O is Li +: Fe 3+=1: 1, the amount of polyethylene glycol is 25～5O0g/molFePO 44H 2O.
Above-mentioned sintering temperature is 300～800 ℃, and sintering time is 1～20h.
Above-mentioned inert atmosphere is an argon gas.
The outstanding feature that the present invention prepares material is:
1. the major part of this material primary raw material source is abundant, cheap.
2. the FePO of one of raw material 44H 2O is as source of iron, and compares as source of iron with ferrous iron, reduced the difficulty of control reaction condition, improved purity, performance and the production efficiency of product.
3. the polyethylene glycol of one of raw material (PEG) is not only carbon source, and the carbon of its decomposition in situ gained has improved the conductivity of material, and as a kind of reducing agent, hydrogen that its decomposition produces and carbon provide strong reduction atmosphere for the generation of product.
4. the present invention mixes reactant, adds deionized water furnishing rheology attitude and makes predecessor, and an one-step baking obtains target product in inert atmosphere afterwards.We claim that the method is a rheological phase reaction.The rheological phase reaction method is the softening synthetic method of a kind of green, environmental protection, low energy consumption.
5. preparation technology of the present invention is simple, and technological parameter is more easy to control, good reproducibility.
6. can make the material of nano-scale particle, be uniformly dispersed function admirable.The lithium ion battery of being made by this material is potential good power sources such as electric motor car, notebook computer.
7. this synthesis technique is adapted to suitability for industrialized production.
Embodiment
The proportion of raw materials of material provided by the present invention is: LiOHH 2O (perhaps Li 2CO 3, CH 3COOLi2H 2O) and FePO 44H 2The mole of O is than being Li +: Fe 3+=1: 1, the amount of the polyethylene glycol of use (PEG) is 25～500g/mo) lFePO 44H 2O.
By said ratio, raw material is mixed, add entry furnishing rheology attitude, sintering obtains LiFePO under inert atmosphere afterwards 4/ C.Sintering temperature is 300～800 ℃, and roasting time is 1～20h.
In a concrete scheme of the present invention, raw materials used is LiOHH 2O, FePO 44H 2O and PEG (molecular weight 10000), ratio is Li +: Fe 3+=1: 1 (mol ratio), 25～500gPEG/mol FePO 44H 2O, used inert atmosphere are argon gas, can obtain well-crystallized's LiFePO 4/ C positive electrode.
In a preferred version of the present invention, raw materials used is LiOHH 2O, FePO 44H 2O and PEG (molecular weight 10000), ratio is Li +: Fe 3+During=1: 1 (mol ratio), every mole of FePO 44H 2O adds 250gPEG, and the chemical property of products therefrom is best.
In a preferred version of the present invention, raw materials used is LiOHH 2O, FePO 44H 2O and PEG (molecular weight 10000), mole is than being Li +: Fe 3+=1: 1,250gPEG/mol FePO 44H 2During O, the temperature range that obtains well-crystallized's product is 500～700 ℃, and the sintering time scope that obtains well behaved product is 6～20h.。
In a concrete scheme of the present invention, raw materials used is LiOHH 2O, FePO 44H 2When O and PEG (molecular weight 1000,2000,4000,6000,20000),, also can obtain well-crystallized's LiFePO by above-mentioned condition roasting 4/ C positive electrode.
In a concrete scheme of the present invention, raw materials used is Li 2CO 3(CH 3COOLi2H 2O), FePO 44H 2When O and PEG (molecular weight 2000),, also can obtain well-crystallized's LiFePO by above-mentioned condition sintering 4/ C positive electrode.
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1
Get LiOHH 2O, FePO 44H 2The mole ratio of O is 1: 1, adds 25,100,250 respectively, 500gPEG (molecular weight 10000)/molFePO 44H 2O.With LiOHH 2O, FePO 44H 2After O and PEG mix, add 100ml/molFePO 44H 2The deionized water furnishing rheology attitude of O, 700 ℃ behind sintering 12h under the argon shield, products therefrom is XRD characterizes, the LiFePO of products therefrom crystal formation and standard 4Collection of illustrative plates conforms to, and carbon is amorphous state, and its existence does not influence the product crystal formation.Testing as can be known by elementary analysis, the general phosphorus content of each product is respectively 0.5,3,6,13wt.%.Get above-mentioned sample respectively, be mixed and made into cathode film with acetylene black and adhesive according to 75: 20: 5 ratio (mass percent), be pressed on the steel mesh, as negative pole, Cellgard 2400 (American) perforated membrane is as barrier film, with 1mol/LLiClO with the lithium sheet 4(EC: DMC=1: 1) as electrolyte, be assembled into simulated battery, on new prestige (Shenzhen) high accuracy battery test macro, carry out electrochemical property test.In current density is to discharge and recharge experiment under the 1C (170A/g), and the discharge capacity first of each sample is respectively 87,126,144 and 99mAh/g, and therefore selecting the PEG optimum addition is 250g/molFePO 44H 2O.Get LiOHH 2O, FePO 44H 2The mole ratio of O is 1: 1, and the amount of PEG (molecular weight 10000) is 250g/mol FePO 44H 2O is as reactant.With LiOHH 2O, FePO 44H 2After O and PEG mix, add 100ml/molFePO 44H 2The deionized water furnishing rheology attitude of O, sintering in argon atmosphere then, temperature range is 300～800 ℃, the time is 12 hours.From the provable LiFePO that in 300～800 ℃ of temperature ranges, all can obtain the well-crystallized of XRD diffraction pattern 4Product illustrates with the rheological phase reaction method and can synthesize at 300 ℃ of target products of low temperature that rheological phase reaction is the synthetic method of low energy consumption.And under these conditions the product particle of sintering be nano level, by grain size analysis test and sem test as can be known granular size be 100～300nm.The sample of getting 300,400,500,600,700,800 ℃ is an example, the chemical property that compares each product, in current density is to discharge and recharge experiment under the 1C (170mA/g), the discharge capacity first of each sample is respectively 110,127,130,144,144,109mAh/g, and therefore to obtain the temperature range of well-crystallized's product be 500～700 ℃ to proof.Get 7 parts of the raw materials of the aforementioned proportion of equivalent, respectively at 600 ℃ of sintering 1,3,6,9,12,15,20 hours in argon gas, the product that obtains is XRD and is characterized the proof products therefrom and be olivine structural and target product LiFePO 4Crystal formation conforms to, and illustrates with the rheological phase reaction method can synthesize target product with 1 hour.The chemical property that compares each product, in current density is to discharge and recharge experiment under the 1C (170mA/g), the discharge capacity first of each sample is respectively 121,134,154,150,144,145,144mAh/g, as can be known at sintering time more than 6 hours the time, the difference of discharge capacity first of product is little.Consider the needs of suitability for industrialized production high efficiency, low energy consumption, we get 6 hours as best sintering time.
Embodiment 2
As weighing positive electrode LiFePO 4The important indicator of/C is exactly its high rate capability, so we get LiOHH 2O, FePO 44H 2The mole ratio of O is 1: 1, and the amount of PEG (molecular weight 10000) is 250g/molFePO 44H 2O adds 80ml/molFePO as reactant 44H 2The deionized water furnishing rheology attitude of O, the product that sintering obtained in 6 hours under 600 ℃ of nitrogen protections is that example illustrates its high rate capability.In active material: acetylene black: adhesive equals 75: 20: 5 ratio (mass percent) and is mixed and made into cathode film, with the lithium sheet as negative pole, with Cellgard2400 (American) perforated membrane as barrier film, with 1MLiClO 4(EC: DMC=1: 1) as electrolyte, be assembled into simulated battery, on new prestige (Shenzhen) the high accuracy battery test macro, carry out electrochemical property test.Be to carry out the charge-discharge performance test under 1C (170mA/g), 2C, the 5C in current density respectively, first discharge capacity be respectively 145,137,124mAh/g, material is through activation process, the passage of ion turnover is progressively unobstructed, the not obviously decay of circulation 100 circle back capacity is respectively 151,142 in the discharge capacities of 100 circles, 124mAh/g.The charging and discharging curve of the above material of circulation 100 circles does not have tangible polarization phenomena, illustrate that this material has very superior high rate capability, it is low to have solved this material electric conductivity, and the shortcoming of chemical property difference under the high current density is adapted to the needs to the high magnification high-voltage battery such as electric motor car.
Embodiment 3
Get LiOHH 2O, FePO 44H 2The mole ratio of O is 1: 1, and the amount of PEG (molecular weight 1000,2000,4000,6000,20000) is 250gPEG/molFePO 44H 2During O, add 150ml/molFePO 44H 2The water furnishing rheology attitude of O, the material that roasting obtained in 6 hours under 600 ℃ of argon shields are done the XRD test, and product is the LiFePO of olivine-type as can be known 4/ C.Illustrate that PEG with different molecular weight does raw material and also can obtain the intact target product of crystal formation.
Embodiment 4
Get Li 2CO 3(perhaps CH 3COOLi2H 2O), FePO 44H 2The mole ratio of O is 1: 1, and the amount of PEG (molecular weight 2000) is 250g/molFePO 44H 2O adds 100ml/molFePO 44H 2The deionized water furnishing rheology attitude of O, the material that sintering obtained in 6 hours under 600 ℃ of nitrogen protections are done the XRD test, and product is the LiFePO of olivine-type as can be known 4/ C.Illustrate that doing raw material with different lithium salts also can obtain the intact product of crystal formation, help suitability for industrialized production the diversity of raw material is selected.

Claims (4)

1. anode material for lithium-ion batteries LiFePO 4The preparation method of/C is characterized in that: with FePO 44H 2O and LiOHH 2O, Li 2CO 3Or CH 3COOLi2H 2O and solid polyethylene glycol mix, and add entry furnishing rheology attitude, and sintering obtains anode material for lithium-ion batteries LiFePO under inert atmosphere then 4/ C.
2. preparation method according to claim 1 is characterized in that: described FePO 44H 2O and LiOHH 2O, Li 2CO 3Or CH 3COOLi2H 2The consumption mol ratio of O is Li +: Fe 3+=1: 1, the amount of polyethylene glycol is 25～500g/mol FePO 44H 2O.
3. preparation method according to claim 1 and 2 is characterized in that: described sintering temperature is 300～800 ℃, and sintering time is 1～20h.
4. preparation method according to claim 1 and 2 is characterized in that: described inert atmosphere is an argon gas.
CNB2006101251248A 2006-11-23 2006-11-23 A method to manufacture anode material of LiFePO4/C for lithium ion cell Expired - Fee Related CN100420074C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101219783B (en) * 2008-01-23 2010-08-11 四川大学 Method for producing electrode material with ferrophosphorus
CN104701499A (en) * 2013-12-06 2015-06-10 天津赫维科技有限公司 Preparation method of lithium iron phosphate/C composite material with high specific surface area
CN105322164A (en) * 2014-07-31 2016-02-10 储能创新驱动有限公司 Process for the preparation of microcrystalline LiFePo4, which is specifically suitable as cathode material in lithium batteries
CN105762343A (en) * 2016-04-17 2016-07-13 郑叶芳 Preparation method of LiFePO4/C anode material by rheological phase method
CN105826557A (en) * 2016-04-17 2016-08-03 台州学院 LiFePO4/C anode material prepared through rheologic phase reaction

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1305147C (en) * 2004-12-30 2007-03-14 清华大学 Method for preparing high-density spherical ferric lithium phosphate as anode material of lithium-ion battery
CN100347081C (en) * 2005-12-29 2007-11-07 上海交通大学 Process for preparing lithium ferrous phosphate coated with carbon

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101219783B (en) * 2008-01-23 2010-08-11 四川大学 Method for producing electrode material with ferrophosphorus
CN104701499A (en) * 2013-12-06 2015-06-10 天津赫维科技有限公司 Preparation method of lithium iron phosphate/C composite material with high specific surface area
CN105322164A (en) * 2014-07-31 2016-02-10 储能创新驱动有限公司 Process for the preparation of microcrystalline LiFePo4, which is specifically suitable as cathode material in lithium batteries
CN105762343A (en) * 2016-04-17 2016-07-13 郑叶芳 Preparation method of LiFePO4/C anode material by rheological phase method
CN105826557A (en) * 2016-04-17 2016-08-03 台州学院 LiFePO4/C anode material prepared through rheologic phase reaction

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