CN101867043A - Method for preparing lithium ion battery anode material of LiFePO4/C - Google Patents

Method for preparing lithium ion battery anode material of LiFePO4/C Download PDF

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Publication number
CN101867043A
CN101867043A CN201010210376A CN201010210376A CN101867043A CN 101867043 A CN101867043 A CN 101867043A CN 201010210376 A CN201010210376 A CN 201010210376A CN 201010210376 A CN201010210376 A CN 201010210376A CN 101867043 A CN101867043 A CN 101867043A
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solution
lifepo4
sintering
soluble
oil bath
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赵金鑫
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Irico Group Corp
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Irico Group Corp
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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 of LiFePO4/C, comprising the following steps: dissolving H3PO4 and soluble compound comprising Li+ and Fe2+ in deionized water, wherein the atomic ratio of Li to Fe to P is 1:1:1; adding ascorbic acid to Fe2+ solution to be used as antioxidant; fully mixing the Fe2+ solution and soluble carbon source solution to obtain homogeneous solution; adjusting the pH value of the homogeneous solution to 6-8.5 by using the LiOH or H3PO4; adding the obtained mixed solution to an oil bath pan and heating the mixed solution until sol to be formed; taking the sol out of the oil bath pan and adding the sol to a vacuum drying box for drying; and sintering the dried product in the protective atmosphere to obtain the nano LiFePO4/C. The particles of the LiFePO4/C which is prepared with the method are in nano size, thus the ion transmission path can be effectively shortened. In addition, the pyrolytic carbon is formed on the surfaces of the particles of the LiFePO4/C, thus the electron transfer efficiency can be improved, and the high-power charge and discharge can be realized.

Description

A kind of anode material for lithium-ion batteries LiFePO 4/ C preparation method
Technical field:
The invention belongs to energy and material preparation technology field, relate to a kind of anode material for lithium-ion batteries LiFePO 4The preparation method of/C.
Background technology:
Lithium rechargeable battery has that voltage height, energy density are big, good cycle, etc. advantage, the nineties sony is widely used after releasing first lithium rechargeable battery from last century, the research and development of lithium rechargeable battery also are subjected to extensive concern.A.K.Padhi reported LiFePO 4 (LiFePO first in 1997 4) have the removal lithium embedded function, because of it has high energy density, cheap price, the characteristics of excellent security, being thought in the industry most possibly becomes EV positive electrode for battery material.When it has prominent advantages, also have its fatal shortcoming as EV positive electrode for battery material: the electrons/ions transfer rate is low to be unfavorable for high-powerly discharging and recharging, cryogenic property is relatively poor.
Current LiFePO 4The synthetic main solid phase method that adopts of material, the products obtained therefrom particle diameter is big and particle size distribution is inhomogeneous, has further limited its electrons/ions transfer rate, is difficult to the stable LiFePO of obtained performance 4Product is with LiFePO for what solve the common employing of the low defective of electrons/ions transfer rate 4Material nanoization and at its coated with carbon promoting its electrons/ions transmission performance, adopt improved solid phase method to synthesize LiFePO for realizing this purpose patent CN101152960A 4, at first with the soluble Fe that contains 2+/ Fe 3+And P 5+Compound precipitation after carry out the solid phase ball milling with lithium-containing compound again and mix, this method is to less LiFePO 4Particle diameter has certain effect but solid phase mixing can not be uniformly distributed in LiFePO with the Li ion 4Material; Patent CN1821063A is for being implemented in LiFePO 4What coated with carbon adopted is the mode of mixing with the abundant spheroidal graphite of carbon source, and the solid phase spheroidal graphite is difficult to the uniformity that carbon is wrapped in realization because of the limitation of itself.
Summary of the invention:
The objective of the invention is to overcome the LiFePO of existing method preparation 4/ C product cut size is big and particle size distribution is inhomogeneous, and the electrons/ions transfer rate is low, and the defective of unstable properties provides a kind of and can obtain concentrated nanometer scale and the high a kind of preparation method of electric transmission rate of being distributed in of granularity.
The object of the present invention is to provide a kind of anode material for lithium-ion batteries LiFePO 4The preparation method of/C.
To achieve these goals, the present invention adopts following technical scheme: a kind of anode material for lithium-ion batteries LiFePO 4The preparation method of/C; with soluble lithium compound; soluble ferrous salt; phosphoric acid is raw material; according to atomic ratio Li: Fe: P=1: respectively be dissolved at 1: 1 and obtain ferrous salt solution in the deionized water; and in ferrous salt solution, add ascorbic acid and fully mix with solvable carbon source solution after as antioxidant and obtain homogeneous phase solution; regulate homogeneous phase solution pH value then and between 6-8.5, obtain mixed solution; place the oil bath pan heating until forming colloidal sol mixed solution; colloidal sol moved into carry out drying in the vacuum drying chamber, dried product carries out sintering and forms under protective atmosphere.
Described soluble ferrous salt is FeSO 47H 2O, FeCl 2Or Fe (NH 4) 2(SO 4) 2, described soluble lithium compound is LiOHH 2O, LiNO 3, LiC 2H 3O 22H 2O or Li 2C 2O 4
Described solvable carbon source solution is polyethylene glycol, dimethyl sulfoxide (DMSO), citric acid, sucrose, rock sugar or glucose.
The pH value of described homogeneous phase solution is between 6-7.5.
The temperature that described mixture places oil bath pan to heat is controlled at 70-100 ℃.
The vacuumize temperature of described colloidal sol is 80-120 ℃.
Described sintering carries out in protective atmosphere, and guard rows gas is N 2, Ar or nitrogen and hydrogen mixture a kind of.
The sintering temperature of described desciccate is 500-950 ℃, and sintering time is more than 1 hour.
Compared with prior art, the present invention has the following advantages: the present invention adopts Prepared by Sol Gel Method LiFePO 4, solved existing prepared LiFePO 4The reactant that adopts ball mill mixing to cause mixes uneven problem, and products therefrom is that nanoscale, even particle size distribution, carbon coat evenly, and it is good to need not the reprocessing processability.
Description of drawings:
Fig. 1 is XRD (X-ray diffraction) image of the embodiment of the invention 1 gained sample;
Fig. 2 is SEM (scanning electron microscopy) image of the embodiment of the invention 1 gained sample;
Embodiment:
Below by specific embodiment the present invention is done detailed description, following embodiment only is used to illustrate the present invention, but and is not used in and limits practical range of the present invention.
Embodiment 1:
With FeSO 47H 2O, LiOHH 2O, H 3PO 4Be raw material, wherein Li: Fe: P=1: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, to FeSO 47H 2Adding amount of substance in the O solution is Fe 2+1 times ascorbic acid solution of amount of substance is with above-mentioned solution and H 3PO 4After solution fully mixes, with LiOHH 2O solution and provide the polyglycol solution of carbon source to add wherein, heating and temperature control is at 80 ℃ in water-bath with gained solution, and regulating its pH is 6, and colloidal sol to be formed is placed on 120 ℃ of freeze-day with constant temperature in the vacuum drying chamber.The gained desiccant gel is put in the alumina crucible at N 2The following 950 ℃ of sintering of atmosphere 1 hour, cooling take out and promptly get LiFePO 4/ C material.
Embodiment 2:
With Fe (NH 4) 2(SO 4) 2, LiOHH 2O, H 3PO 4Be raw material, wherein Li: Fe: P=1: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, to Fe (NH 4) 2(SO 4) 2Adding amount of substance in the solution is Fe 2+2 times ascorbic acid solution of amount of substance is with above-mentioned solution and H 3PO 4After solution fully mixes, with LiOHH 2O solution and provide the dimethyl sulphoxide solution of carbon source to add wherein, heating and temperature control is at 100 ℃ in water-bath with gained solution, and regulating its pH is 7, and colloidal sol to be formed is placed on 100 ℃ of freeze-day with constant temperature in the vacuum drying chamber.The gained desiccant gel was put in the alumina crucible under Ar atmosphere 800 ℃ of sintering 1.5 hours, and cooling is taken out and is promptly got LiFePO 4/ C material.
Embodiment 3:
With Fe (NH 4) 2(SO 4) 2, LiNO 3, H 3PO 4Be raw material, wherein Li: Fe: P=1: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, to Fe (NH 4) 2(SO 4) 2Adding amount of substance in the solution is Fe 2+2 times ascorbic acid solution of amount of substance is with above-mentioned solution and H 3PO 4After solution fully mixes, with LiNO 3Solution and provide the sucrose solution of carbon source to add wherein, heating and temperature control is at 90 ℃ in water-bath with gained solution, and regulating its pH is 7.5, and colloidal sol to be formed is placed on 110 ℃ of freeze-day with constant temperature in the vacuum drying chamber.The gained desiccant gel is put in the alumina crucible at N 2/ H 2The following 500 ℃ of sintering of=9: 1 atmosphere 5 hours, cooling take out and promptly get LiFePO 4/ C material.
Embodiment 4:
With FeCl 2, LiC 2H 3O 22H 2O, H 3PO 4Be raw material, wherein Li: Fe: P=1: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, to FeCl 2Adding amount of substance in the solution is Fe 2+1 times ascorbic acid solution of amount of substance is with above-mentioned solution and H 3PO 4After solution fully mixes, with LiC 2H 3O 22H 2O solution and provide the citric acid solution of carbon source to add wherein, heating and temperature control is at 70 ℃ in water-bath with gained solution, and regulating its pH is 8.5, and colloidal sol to be formed is placed on 100 ℃ of freeze-day with constant temperature in the vacuum drying chamber.The gained desiccant gel is put in the alumina crucible at N 2The following 500 ℃ of sintering of atmosphere 5 hours, cooling take out and promptly get LiFePO 4/ C material.
Embodiment 5:
With FeSO 47H 2O, Li 2C 2O 4, H 3PO 4Be raw material, wherein Li: Fe: P=1: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, to FeSO 47H 2Adding amount of substance in the O solution is Fe 2+1 times ascorbic acid solution of amount of substance is with above-mentioned solution and H 3PO 4After solution fully mixes, with Li 2C 2O 4Solution and provide the glucose solution of carbon source to add wherein, heating and temperature control is at 100 ℃ in water-bath with gained solution, and regulating its pH is 7, and colloidal sol to be formed is placed on 80 ℃ of freeze-day with constant temperature in the vacuum drying chamber.The gained desiccant gel is put in the alumina crucible at N 2/ H 2The following 600 ℃ of sintering of atmosphere 10 hours, cooling take out and promptly get LiFePO 4/ C material.
Above content is to further describing that the present invention did in conjunction with concrete preferred implementation; can not assert that the specific embodiment of the present invention only limits to this; for the general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by claims of being submitted to.

Claims (8)

1. anode material for lithium-ion batteries LiFePO 4The preparation method of/C; it is characterized in that: with soluble lithium compound; soluble ferrous salt; phosphoric acid is raw material; according to atomic ratio Li: Fe: P=1: respectively be dissolved at 1: 1 and obtain ferrous salt solution in the deionized water; and in ferrous salt solution, add ascorbic acid and fully mix with solvable carbon source solution after as antioxidant and obtain homogeneous phase solution; regulate homogeneous phase solution pH value then and between 6-8.5, obtain mixed solution; place the oil bath pan heating until forming colloidal sol mixed solution; colloidal sol moved into carry out drying in the vacuum drying chamber, dried product carries out sintering and forms under protective atmosphere.
2. the method for claim 1, it is characterized in that: described soluble ferrous salt is FeSO 47H 2O, FeCl 2Or Fe (NH 4) 2(SO 4) 2, described soluble lithium compound is LiOHH 2O, LiNO 3, LiC 2H 3O 22H 2O or Li 2C 2O 4
3. the method for claim 1, it is characterized in that: described solvable carbon source solution is polyethylene glycol, dimethyl sulfoxide (DMSO), citric acid, sucrose, rock sugar or glucose.
4. the method for claim 1, it is characterized in that: the pH value of described homogeneous phase solution is between 6-7.5.
5. the method for claim 1, it is characterized in that: the temperature that described mixture places oil bath pan to heat is controlled at 70-100 ℃.
6. the method for claim 1, it is characterized in that: the vacuumize temperature of described colloidal sol is 80-120 ℃.
7. the method for claim 1, it is characterized in that: described sintering carries out in protective atmosphere, and guard rows gas is N 2, Ar or nitrogen and hydrogen mixture a kind of.
8. the method for claim 1, it is characterized in that: the sintering temperature of described desciccate is 500-950 ℃, sintering time is more than 1 hour.
CN201010210376A 2010-06-28 2010-06-28 Method for preparing lithium ion battery anode material of LiFePO4/C Pending CN101867043A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103682344A (en) * 2013-12-25 2014-03-26 天津斯特兰能源科技有限公司 Method for synthetizing lithium iron phosphate material by utilizing sol-gel method
CN103715427A (en) * 2013-12-25 2014-04-09 天津斯特兰能源科技有限公司 Preparation method for lithium iron phosphate nano single-crystal material
CN105098145A (en) * 2015-09-15 2015-11-25 常州市鼎日环保科技有限公司 Preparation method of regular diamond lithium iron phosphate powder cathode material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1907844A (en) * 2006-08-11 2007-02-07 广州市鹏辉电池有限公司 High density ultrafine composite ferric lithium phosphate anode material and preparation method
CN1971981A (en) * 2006-12-14 2007-05-30 南开大学 High charge-discharge magnification lithium iron phosphate material used for anode of lithium ion battery and its preparation method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1907844A (en) * 2006-08-11 2007-02-07 广州市鹏辉电池有限公司 High density ultrafine composite ferric lithium phosphate anode material and preparation method
CN1971981A (en) * 2006-12-14 2007-05-30 南开大学 High charge-discharge magnification lithium iron phosphate material used for anode of lithium ion battery and its preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《化工新型材料》 20070930 李庆余等 纳米LiFePO4C复合正极材料的制备及其性能研究 3-7 1-8 第35卷, 第9期 2 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103682344A (en) * 2013-12-25 2014-03-26 天津斯特兰能源科技有限公司 Method for synthetizing lithium iron phosphate material by utilizing sol-gel method
CN103715427A (en) * 2013-12-25 2014-04-09 天津斯特兰能源科技有限公司 Preparation method for lithium iron phosphate nano single-crystal material
CN103715427B (en) * 2013-12-25 2016-01-13 天津斯特兰能源科技有限公司 The preparation method of lithium iron phosphate nano single-crystal material
CN105098145A (en) * 2015-09-15 2015-11-25 常州市鼎日环保科技有限公司 Preparation method of regular diamond lithium iron phosphate powder cathode material

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Application publication date: 20101020