CN101777649A - Preparation method of lithium iron phosphate of positive electrode material of lithium ion battery - Google Patents

Preparation method of lithium iron phosphate of positive electrode material of lithium ion battery Download PDF

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CN101777649A
CN101777649A CN201010124302A CN201010124302A CN101777649A CN 101777649 A CN101777649 A CN 101777649A CN 201010124302 A CN201010124302 A CN 201010124302A CN 201010124302 A CN201010124302 A CN 201010124302A CN 101777649 A CN101777649 A CN 101777649A
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preparation
lithium
ion battery
lithium ion
solution
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention provides a preparation method of lithium iron phosphate of positive electrode materials of lithium ion batteries. The lithium iron phosphate has a chemical formula of LiFePO4. The preparation method of the lithium iron phosphate comprises the following steps: using dissoluble compounds containing Fe<2+> as iron sources, then, mixing the iron sources with H3PO4 and dissoluble compounds containing Li<+> according to the mass ratio of Li/Fe/P=1.5 to 3.5/1/1 to obtain a homogeneous solution; adding carbamide in the solution to be used as a pH value regulating agent; adding ascorbic acid as oxidation inhibitors; placing the obtained mixed solution into a water bath pot to be heated; stirring the obtained mixed solution by a magnetic stirring apparatus until the pH value is in a range between 6 and 8 to obtain active ingredient precipitates; washing the precipitates; drying the precipitates at a low temperature; taking out materials after the drying completion; and sintering the materials under in the protection atmosphere to obtain LiFePO4 materials. The lithium iron phosphate prepared by the method of the invention has concentrated grain fineness distribution and good degree of crystallinity.

Description

A kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery
Technical field
The invention belongs to the energy and material technical field, relate to a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery.
Background technology
Report LiFePO 4 (LiFePO first from A.K.Padhi in 1997 4) have the removal lithium embedded function, because of it has high energy density, cheap price, the characteristics of excellent security, be a kind of outstanding power lithium-ion battery positive electrode, be subjected to the extensive concern of energy field.
Leading enterprise in the LiFePO 4 field mainly contains 3 families in the world at present, is respectively the Valence of the A123 of the U.S., Canadian Phostech and the U.S., grasps comparatively ripe volume production technology.The production capacity of present three large manufacturers is about 4000 tons/year.1997, ferrousphosphate lithium material began to cause domestic concern.1998, national 863 Program invested 2,000,000,000 at Shantou research LiFePO 4.Chinese Enterprise starts the ferrousphosphate lithium material exploitation successively since calendar year 2001, and current, domestic LiFePO 4 industrial investment heat is risen, and it has a extensive future, and market potential is huge.
The synthetic ferrous phosphate reason of conventional method exists the problem that purity is not high, particle size distribution is not concentrated, tap density is low, crystallization is bad when having a bright future, and has restricted the large-scale application of LiFePO 4.
Summary of the invention
The object of the present invention is to provide a kind of acquisition particle size distribution to concentrate, the preparation method of the ferrous phosphate reason of better crystallinity degree.
To achieve these goals, the present invention adopts following technical scheme: a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery, the chemical formula of described LiFePO 4 is: LiFePO 4, its preparation method is to contain Fe 2+Soluble compounds be source of iron, again and H 3PO 4And contain Li +Soluble compounds according to the ratio Li of amount of substance: Fe: P=1.5-3.5: obtain homogeneous phase solution after mixing at 1: 1; in above-mentioned solution, add urea as Ph value conditioning agent; add ascorbic acid as antioxidant; the gained mixed solution is placed water-bath heating and obtains the active ingredient precipitation in the stirring of magnetic stirring apparatus after Ph value scope is 6-8; with the low temperature drying of sediment washing back, to be dried finish take out and under protective atmosphere sintering promptly obtain LiFePO 4Material.
Described Fe 2+Soluble compounds be FeSO 47H 2O, FeCl 2, Fe (NH 4) 2(SO 4) 2In a kind of, the described Li that contains +Soluble compounds be LiOHH 2O, LiNO 3, a kind of among the LiCl.
The amount of substance of described urea is more than 10 times of amount of substance of all metal ions in the described homogeneous phase solution.
The consumption of described ascorbic acid is Fe in the solution 2+The 2-5 of amount of substance doubly.
The heating-up temperature of described water-bath is 60-90 ℃.
Described its volume is more than 5 times of sediment volume to sedimentary washing employing deionized water, and washing times is more than 3 times.
Described the sediment low temperature drying is carried out in vacuum drying chamber, the low temperature drying temperature is below 40 ℃.
Protective gas in the described sintering process is N 2, Ar, volume ratio be 9: 1 N 2/ H 2Mist, volume ratio are 3: 1 N 2/ H 2A kind of in the mist.
The temperature of described sintering is in 500-850 ℃ of scope.
Described sintering time is 2-6 hour.
Compared with prior art, the present invention has the following advantages: the present invention adopts urea as the Ph conditioning agent, its advantage is fully to mix with reaction solution in the mode of solution as the urea molecule of Ph conditioning agent, urea slowly decomposes under the mild reaction conditions of water-bath heating, generates ammoniacal liquor and play the effect of regulating Ph in entire reaction solution scope.It is the internal control formula that the present invention changes external control type Ph control method, and the variation of Ph value is gentle more, has avoided adding in the conventional coprecipitation reaction solution and the Ph conditioning agent contact interface Ph of the place vary within wide limits that the Ph conditioning agent causes and has been easy to generate very easily oxidized Fe (OH) 2Precipitation, this method has been avoided the inhomogeneous of precipitate nucleation particle diameter that the variation of Ph value causes greatly simultaneously.The ferrousphosphate lithium material of concentrating for the prepared sizes distribution lays the foundation, to gained sediment LiFePO 4Carry out sintering and avoided spray drying process gained sample degree of crystallinity bad, and the problem of the easy oxidation of sample in the spray process.
Description of drawings
Fig. 1 is the XRD of embodiment 1 gained sample (X-ray diffraction) image.
Fig. 2 is with the SEM of embodiment 1 gained sample (scanning electron microscopy) image.
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=3: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, with FeSO 47H 2O solution and H 3PO 4After solution fully mixes, with LiOHH 2O solution adds wherein, fully mixes obtaining homogeneous phase solution, and adding amount of substance in this solution is Fe 2+4 times the ascorbic acid solution and the amount of substance of amount of substance are the urea liquids of 15 times of all metal ions amount of substance summations, fully mix.With gained solution move into flask in water-bath heating and temperature control at 80 ℃, and do not stop to stir with magnetic stirring apparatus, treat that after this solution Ph will wash 3 with 5 times of deionized waters to its volume behind the product suction filtration at 6 o'clock, placed 40 ℃ of freeze-day with constant temperature of vacuum drying chamber.The gained desciccate is put in the alumina crucible at N 2/ H 2The following 600 ℃ of sintering of=9: 1 atmosphere 4 hours, cooling take out and promptly get LiFePO 4Material.
Embodiment 2:
With FeCl, LiNO 3, H 3PO 4Be raw material, wherein Li: Fe: P=1.5: 1: 1, mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, with FeCl solution and H 3PO 4After solution fully mixes, with LiNO 3Solution adds wherein, fully mixes obtaining homogeneous phase solution, and adding amount of substance in this solution is Fe 2+3 times the ascorbic acid solution and the amount of substance of amount of substance are the urea liquids of 25 times of all metal ions amount of substance summations, fully mix.With gained solution move into flask in water-bath heating and temperature control at 60 ℃, and do not stop to stir with magnetic stirring apparatus, treat solution Ph be 7.5 o'clock with after washing 4 times with 6 times of deionized waters behind the product suction filtration to its volume, place 35 ℃ of freeze-day with constant temperature of vacuum drying chamber.The gained desciccate is put in the alumina crucible at N 2/ H 2The following 850 ℃ of sintering of=3: 1 atmosphere 2 hours, cooling take out and promptly get LiFePO 4Material.
Embodiment 3:
With Fe (NH 4) 2(SO 4) 2, LiNO 3, H 3PO 4Be raw material, wherein Li: Fe: P=2: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, with Fe (NH 4) 2(SO 4) 2Solution and H 3PO 4After solution fully mixes, with LiNO 3Solution adds wherein, fully mixes obtaining homogeneous phase solution, and adding amount of substance in this solution is Fe 2+3 times the ascorbic acid solution and the amount of substance of amount of substance are the urea liquids of 20 times of all metal ions amount of substance summations, fully mix.With gained solution move into flask in water-bath heating and temperature control at 90 ℃, and do not stop to stir with magnetic stirring apparatus, treat that after this solution Ph will wash 5 with 8 times of deionized waters to its volume behind the product suction filtration at 6.5 o'clock, placed 30 ℃ of freeze-day with constant temperature of vacuum drying chamber.The gained desciccate is put in the alumina crucible at N 2Following 700 ℃ of sintering of atmosphere 3 hours, cooling is taken out and is promptly got LiFePO 4Material.
Embodiment 4:
With Fe (NH 4) 2(SO 4) 2, LiOHH 2O, H 3PO 4Be raw material, wherein Li: Fe: P=3.5: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, with Fe (NH 4) 2(SO 4) 2Solution and H 3PO 4After solution fully mixes, with LiOHH 2O solution adds wherein, fully mixes obtaining homogeneous phase solution, and adding amount of substance in this solution is Fe 2+5 times the ascorbic acid solution and the amount of substance of amount of substance are the urea liquids of 30 times of all metal ions amount of substance summations, fully mix.With gained solution move into flask in water-bath heating and temperature control at 90 ℃, and do not stop to stir with magnetic stirring apparatus, treat that after this solution Ph will wash 5 with 6 times of deionized waters to its volume behind the product suction filtration at 7.5 o'clock, placed 20 ℃ of freeze-day with constant temperature of vacuum drying chamber.The gained desciccate was put in the alumina crucible under the atmosphere of Ar 500 ℃ of sintering 6 hours, and cooling is taken out and is promptly got LiFePO 4Material.
Embodiment 5:
With FeCl 2, LiOHH 2O, H 3PO 4Be raw material, wherein Li: Fe: P=3: 1: 1.Mentioned reagent is dissolved in respectively obtains transparent homogeneous phase solution in the deionized water, with FeCl 2Solution and H 3PO 4After solution fully mixes, with LiOHH 2O solution adds wherein, fully mixes obtaining homogeneous phase solution, and adding amount of substance in this solution is Fe 2+2 times the ascorbic acid solution and the amount of substance of amount of substance are the urea liquids of 25 times of all metal ions amount of substance summations, fully mix.With gained solution move into flask in water-bath heating and temperature control at 70 ℃, and do not stop to stir with magnetic stirring apparatus, treat that after this solution Ph will wash 3 with 15 times of deionized waters to its volume behind the product suction filtration at 8 o'clock, placed 20 ℃ of freeze-day with constant temperature of vacuum drying chamber.The gained desciccate is put in the alumina crucible at N 2/ H 2The following 850 ℃ of sintering of=3: 1 atmosphere 6 hours, cooling take out and promptly get LiFePO 4Material.

Claims (10)

1. the preparation method of a lithium ferrous phosphate as anode material of lithium ion battery, it is characterized in that: the chemical formula of described LiFePO 4 is: LiFePO 4, its preparation method is to contain Fe 2+Soluble compounds be source of iron, again and H 3PO 4And contain Li +Soluble compounds according to the ratio Li of amount of substance: Fe: P=1.5-3.5: obtain homogeneous phase solution after mixing at 1: 1; in above-mentioned solution, add urea as Ph value conditioning agent; add ascorbic acid as antioxidant; the gained mixed solution is placed water-bath heating and obtains the active ingredient precipitation in the stirring of magnetic stirring apparatus after Ph value scope is 6-8; with the low temperature drying of sediment washing back, to be dried finish take out and under protective atmosphere sintering promptly obtain LiFePO 4Material.
2. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that: described Fe 2+Soluble compounds be FeSO 47H 2O, FeCl 2, Fe (NH 4) 2(SO 4) 2In a kind of, the described Li that contains +Soluble compounds be LiOHH 2O, LiNO 3, a kind of among the LiCl.
3. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that: the amount of substance of described urea is more than 10 times of amount of substance of all metal ions in the described homogeneous phase solution.
4. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that: the consumption of described ascorbic acid is Fe in the solution 2+The 2-5 of amount of substance doubly.
5. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that: the heating-up temperature of described water-bath is 60-90 ℃.
6. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that: described deionized water is adopted in sedimentary washing, its volume is more than 5 times of sediment volume, and washing times is more than 3 times.
7. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1 is characterized in that: described the sediment low temperature drying is carried out in vacuum drying chamber, the low temperature drying temperature is below 40 ℃.
8. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that: the protective gas in the described sintering process is N 2, Ar, volume ratio be 9: 1 N 2/ H 2Mist, volume ratio are 3: 1 N 2/ H 2A kind of in the mist.
9. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that: the temperature of described sintering is in 500-850 ℃ of scope.
10. a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery according to claim 1, it is characterized in that: described sintering time is 2-6 hour.
CN201010124302A 2010-03-15 2010-03-15 Preparation method of lithium iron phosphate of positive electrode material of lithium ion battery Pending CN101777649A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014026498A1 (en) * 2012-08-14 2014-02-20 北京彤程创展科技有限公司 Preparation method for organic thiosulfate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1208241C (en) * 2003-02-17 2005-06-29 郑绵平 Wet chemistry method for preparing lithium iron phosphate
CN101355162A (en) * 2007-07-27 2009-01-28 日本化学工业株式会社 Method for manufacturing lithium-iron-phosphorus compound oxide carbon complex and method for manufacturing coprecipitate containing lithium, iron, and phosphorus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1208241C (en) * 2003-02-17 2005-06-29 郑绵平 Wet chemistry method for preparing lithium iron phosphate
CN101355162A (en) * 2007-07-27 2009-01-28 日本化学工业株式会社 Method for manufacturing lithium-iron-phosphorus compound oxide carbon complex and method for manufacturing coprecipitate containing lithium, iron, and phosphorus

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014026498A1 (en) * 2012-08-14 2014-02-20 北京彤程创展科技有限公司 Preparation method for organic thiosulfate
KR20150042281A (en) * 2012-08-14 2015-04-20 베이징 레드 애비뉴 이노바 씨오., 엘티디. Preparation method for organic thiosulfate
KR102037196B1 (en) * 2012-08-14 2019-10-28 베이징 레드 애비뉴 이노바 씨오., 엘티디. Preparation method for organic thiosulfate

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Application publication date: 20100714