CN100347081C - Process for preparing lithium ferrous phosphate coated with carbon - Google Patents

Process for preparing lithium ferrous phosphate coated with carbon Download PDF

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CN100347081C
CN100347081C CNB2005101122115A CN200510112211A CN100347081C CN 100347081 C CN100347081 C CN 100347081C CN B2005101122115 A CNB2005101122115 A CN B2005101122115A CN 200510112211 A CN200510112211 A CN 200510112211A CN 100347081 C CN100347081 C CN 100347081C
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iron phosphate
lifepo
carbon
lithium
gas
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CN1821062A (en
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王久林
王延强
杨军
努丽燕娜
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Shanghai Jiaotong University
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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
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Abstract

The present invention discloses a method for preparing lithium iron phosphate coated with carbon. Iron phosphate is used as raw materials, and the lithium iron phosphate coated with carbon is prepared by a method for carrying out reduction and high-temperature heat treatment in solution. Thereby, the obtained lithium iron phosphate coated with carbon has a good crystal structure and shows good electrochemical performance in a lithium battery. Charge and discharge capacity achieves 167 mAh/g with 0.2C current and approaches to a 170 mAh/g theoretical value. Because the method uses the iron phosphate as the raw materials, the present invention has the advantages of low raw material cost and processing cost and simple technology line and is suitable for scale production.

Description

A kind of preparation method of LiFePO 4 of carbon coated
Technical field
The present invention relates to the preparation method of a kind of preparation method's of mineral compound, particularly a kind of carbon coated LiFePO 4, it is used as the positive electrode material of lithium ion battery.
Background technology
Ferrousphosphate lithium material (LiFePO 4) have abundant raw material, outstanding advantages such as cost is low, specific storage is higher, environmentally friendly, nontoxic, Heat stability is good, become the research focus of various countries' researcher day by day, be a kind of lithium ion cell positive equivalent material of future generation that has much potentiality.The preparation method of ferrousphosphate lithium material mainly contains solid phase method, liquid phase method, microwave method and solid-liquid method mutually at present.
Solid phase method: mention among the Japanese Patent JP2000294238 Ferrox, Secondary ammonium phosphate and Quilonum Retard are carried out the ball milling mixing in acetone, and evaporate under nitrogen, thermal treatment obtains LiFePO 4 under 300-790 ℃ temperature afterwards.People such as A.K.Padhi (J.Electrochem.Soc.1997 (144): be raw material 1188),, obtain ferrousphosphate lithium material at 800 ℃ of sintering again 300-500 ℃ of pre-thermolysis with Quilonum Retard, Iron diacetate, primary ammonium phosphate.
Liquid phase method comprises sol-gel processing, coprecipitation method, hydrothermal synthesis method etc.
Sol-gel processing: by compatible Li +, Fe 2+Or Fe 3+, PO 4 3-The aqueous solution select suitable organic agent that boils together, make it to add thermosetting colloidal sol and gel, obtain LiFePO 4 by sintering then.The existence that this method shortcoming is organic agent that boils together makes carbon content higher.
Coprecipitation method: lithium hydroxide is joined in the solution that contains ferrous ion and phosphoric acid, obtain post precipitation and make by sintering again.As with (NH 4) 2Fe (SO 4) 26H 2O, H 3PO 4, LiOH is raw material, water co-precipitation in the aqueous solution obtains throw out under the nitrogen protection, the compressing tablet roasting obtains product.
Hydrothermal synthesis method: the aqueous solution of tertiary iron phosphate, Trilithium phosphate is put into the autoclave of logical argon gas, and heating 1 hour is synthetic under 220 ℃, 2.4MPa condition.This method synthetic material electric conductivity is little, needs subsequent disposal, and needs high pressure high stable condition.
Microwave method: mention in the Chinese patent 200310121453.1 and adopt Quilonum Retard, Ferrox, primary ammonium phosphate, made the dispersion agent ball milling 4-12 hour, place crucible, put into 3-30 minute microwave oven treatment time to obtain ferrousphosphate lithium material with acetone.
For ferrousphosphate lithium material itself, the subject matter that exists comprises that electric conductivity is low at present.The method of improving the specific conductivity of LiFePO 4 concentrate on element doping and (or) surperficial coated with conductive material.
Solid reaction process is an industry member material preparation method commonly used, has for example successfully prepared LiCoO 2Material.But solid state reaction is solid/liquid/solid interface reaction basically, and reaction interface is little, so long reaction time, and needs repeatedly sintering, promptly grinds sintering again behind the sintering, and technology is loaded down with trivial details, the cycle is long.Even can not guarantee like this to react completely, in the high-temperature reaction process, may generate dystectic Trilithium phosphate Li 3PO 4With ferrous phosphate Fe 3(PO 4) 2, remaining unreacted impurity will worsen the chemical property of ferrousphosphate lithium material, and cause the consistence of material of different batches poor.And simple liquid phase reaction as sol-gel method, is beneficial to and reacts completely, but income is little, is feasible at the prepared in laboratory sample, tooling cost height during suitability for industrialized production.
Summary of the invention
Purpose of the present invention provides a kind of preparation method of LiFePO 4 of carbon coated, is raw material with the tertiary iron phosphate, and the method for reduction and high-temperature heat treatment prepares the LiFePO 4 of carbon coated in the employing solution.
The concrete preparation method of the LiFePO 4 of a kind of carbon coated of the present invention is as follows:
(1) takes by weighing tertiary iron phosphate, lithium acetate and reductive agent and mixing, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, the mol ratio of tertiary iron phosphate and reductive agent is 2: 1 to 1: 5, add distilled water again, make the dissolving of lithium acetate and reductive agent, stir 1 to 10 hour down to evaporate to dryness at 20 ℃ to 90 ℃ then, obtain lithium iron phosphate precursor;
(2) under gas shield, lithium iron phosphate precursor was handled 0.5 to 5 hour at 300 to 800 ℃, obtain LiFePO 4;
(3) take by weighing LiFePO 4 and carbon source and mixing; the mass ratio of LiFePO 4 and carbon source is 99: 1 to 85: 15, carbon source is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness, then under gas shield; handled 0.5 to 5 hour at 500 to 800 ℃, obtain the LiFePO 4 of carbon coated.
The gas that the present invention uses is the mixed gas of argon gas, nitrogen, argon gas and hydrogen or the mixed gas of nitrogen and hydrogen, and hydrogen volume content is 2 to 50% in the mixed gas.
The carbon source that the present invention uses is sucrose, glucose, fructose or lactose.
Reductive agent used in the present invention is ethylene glycol, glycerol, urea, xitix, formaldehyde or turps.
The preparation method of the LiFePO 4 of a kind of carbon coated of the present invention has following characteristics:
It is raw material that the present invention adopts tertiary iron phosphate, in solution, pass through high-temperature heat treatment again after the reduction after, obtain the ferrous phosphate doping lithium anode material of the high-performance carbon coated that lithium ion battery uses.The LiFePO 4 of carbon coated charge/discharge capacity under the 0.2C electric current reaches 167mAh/g, near theoretical value 170mAh/g, has promptly eliminated the influence of unreacted impurity effectively.The employing tertiary iron phosphate is starting material, and material cost and tooling cost are low, and operational path is simple, the cycle is short, energy consumption is low, very suitable scale volume production.
Description of drawings
Fig. 1 is the XRD spectra of LiFePO 4 of the carbon coated of embodiment 2.
Fig. 2 is the LiFePO 4 of carbon coated of embodiment 3 preparation during as anode material for lithium-ion batteries, the charging and discharging curve of battery.
Embodiment
The following examples are to further specify of the present invention, but do not limit the scope of the invention.
Embodiment 1
(1) take by weighing tertiary iron phosphate, lithium acetate and ethylene glycol, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, and the mol ratio of tertiary iron phosphate and ethylene glycol is 1: 1, add distilled water, make the dissolving of lithium acetate and ethylene glycol, stir 10 hours to evaporate to dryness down at 60 ℃ then, obtain lithium iron phosphate precursor.
(2) under nitrogen protection, lithium iron phosphate precursor was handled 5 hours at 650 ℃, obtain LiFePO 4.
(3) take by weighing LiFePO 4 and sucrose, the two mass ratio is 95: 5, sucrose is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness.The protection of nitrogen and volume content 5% hydrogen mixed gas was handled 3 hours at 800 ℃ down then, obtained the LiFePO 4 of carbon coated.
Embodiment 2
(1) take by weighing tertiary iron phosphate, lithium acetate and glycerol, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, and the mol ratio of tertiary iron phosphate and glycerol is 1: 2, add distilled water, make the dissolving of lithium acetate and glycerol, stir 8 hours to evaporate to dryness down at 70 ℃ then, obtain lithium iron phosphate precursor.
(2) under argon gas and the protection of volume content 5% hydrogen mixed gas, lithium iron phosphate precursor was handled 2 hours at 500 ℃, obtained LiFePO 4.
(3) take by weighing LiFePO 4 and glucose, the two mass ratio is 90: 10, glucose is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness.The protection of argon gas and volume content 5% hydrogen mixed gas was handled 4 hours at 700 ℃ down then, obtained the LiFePO 4 of carbon coated.
Fig. 1 is the XRD spectra of the LiFePO 4 of carbon coated, and the result shows that the LiFePO 4 of carbon coated has good crystalline structure.
Embodiment 3
(1) take by weighing tertiary iron phosphate, lithium acetate and urea, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, and the mol ratio of tertiary iron phosphate and urea is 1: 3, add distilled water, make the dissolving of lithium acetate and urea, stir 6 hours to evaporate to dryness down at 80 ℃ then, obtain lithium iron phosphate precursor.
(2) under argon gas and the protection of volume content 5% hydrogen mixed gas, lithium iron phosphate precursor was handled 3 hours at 700 ℃, obtained LiFePO 4.
(3) take by weighing LiFePO 4 and sucrose, the two mass ratio is 92: 8, sucrose is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness.The protection of argon gas and volume content 5% hydrogen mixed gas was handled 2 hours at 650 ℃ down then, obtained the LiFePO 4 of carbon coated.
Embodiment 4
The LiFePO 4 of the carbon coated that embodiment 3 is prepared and conductive agent acetylene black, caking agent ptfe emulsion uniform mixing in ethanolic soln, the mass ratio of LiFePO 4, acetylene black and caking agent is 80: 10: 10, compressing tablet makes positive pole to aluminium foil then.Adopt metallic lithium as negative pole, 1mol/L lithium hexafluoro phosphate (LiPF 6) NSC 11801 and the solution of methylcarbonate as electrolytic solution, porous polyethylene (PE) film that 20 μ m are thick is a barrier film, is assembled into lithium cell, adopts the 0.2C electric current to carry out charge-discharge test, obtain the charging and discharging curve of the ferrous phosphate doping lithium anode material of carbon coated, as shown in Figure 2.The initial charge capacity is 176mAh/g, and loading capacity is 167mAh/g, near the theoretical loading capacity 170mAh/g of ferrous phosphate doping lithium anode material.

Claims (2)

1, a kind of preparation method of LiFePO 4 of carbon coated is characterized in that the preparation method is as follows:
(1) takes by weighing tertiary iron phosphate, lithium acetate and reductive agent and mixing, the mol ratio of tertiary iron phosphate and lithium acetate is 1: 1, the mol ratio of tertiary iron phosphate and reductive agent is 2: 1 to 1: 5, add distilled water again, make the dissolving of lithium acetate and reductive agent, stir 1 to 10 hour down to evaporate to dryness at 20 ℃ to 90 ℃ then, obtain lithium iron phosphate precursor; Wherein reductive agent is ethylene glycol, glycerol, urea, xitix, formaldehyde or turps;
(2) under gas shield, lithium iron phosphate precursor was handled 0.5 to 5 hour at 300 to 800 ℃, obtain LiFePO 4;
(3) take by weighing LiFePO 4 and carbon source and mixing, the mass ratio of LiFePO 4 and carbon source is 99: 1 to 85: 15, carbon source is dissolved in the distilled water and heated and stirred is mixed to evaporate to dryness, then under gas shield, handled 0.5 to 5 hour at 500 to 800 ℃, obtain the LiFePO 4 of carbon coated; Wherein carbon source is sucrose, glucose, fructose or lactose.
2, the preparation method of the LiFePO 4 of a kind of carbon coated according to claim 1 is characterized in that gas is the mixed gas of argon gas, nitrogen, argon gas and hydrogen or the mixed gas of nitrogen and hydrogen, and hydrogen volume content is 2 to 50% in the mixed gas.
CNB2005101122115A 2005-12-29 2005-12-29 Process for preparing lithium ferrous phosphate coated with carbon Expired - Fee Related CN100347081C (en)

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Cited By (1)

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CN102709558A (en) * 2012-06-08 2012-10-03 中南大学 Method for preparing lithium iron phosphate from vivianite

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CN100389062C (en) * 2006-09-07 2008-05-21 上海交通大学 Method for preparing composite material of carbon coated lithium ferrous phosphate through iron phosphate
CN100420074C (en) * 2006-11-23 2008-09-17 武汉大学 A method to manufacture anode material of LiFePO4/C for lithium ion cell
CA2569991A1 (en) * 2006-12-07 2008-06-07 Michel Gauthier C-treated nanoparticles and agglomerate and composite thereof as transition metal polyanion cathode materials and process for making
CN101333650B (en) * 2007-06-27 2010-08-11 中国科学院金属研究所 Method for uniformly and controllably coating conducting carbon layer at surface of LiFePO4 granule surface
FR2932396A1 (en) * 2008-06-11 2009-12-18 Centre Nat Rech Scient Preparing inorganic oxide, used e.g. as pigment, comprises at least partially dissolving inorganic oxide precursor in liquid medium and heating the resulting solution to precipitate oxide, where the solution contains e.g. oxide precursor
CN101798075B (en) * 2009-04-02 2011-06-22 宜昌欧赛科技有限公司 Method for preparing positive electrode material lithium iron phosphate of lithium ion battery
CN101969118A (en) * 2010-10-13 2011-02-09 武汉大学 Method for synthesizing carbon-coated lithium iron phosphate of lithium ion battery cathode material
CN102005565B (en) * 2010-11-06 2015-05-13 合肥国轩高科动力能源股份公司 Method for preparing carbon-coated lithium iron phosphate nanoparticles
CN102134064A (en) * 2011-04-28 2011-07-27 中国科学院新疆理化技术研究所 Preparation method of positive material of lithium iron phosphate
TW201311547A (en) * 2011-08-03 2013-03-16 Murata Manufacturing Co Iron lithium phosphate preparation method, electrode active material, and secondary battery
CN104347880A (en) * 2014-10-14 2015-02-11 东莞新能源科技有限公司 Lithium ion battery capable of quick charging
CN107195902A (en) * 2017-06-01 2017-09-22 桂林理工大学 A kind of trbasic zinc phosphate/carbon compound cathode materials
CN109148878B (en) * 2018-09-03 2020-02-14 东莞塔菲尔新能源科技有限公司 Method for treating residual lithium on surface of lithium-containing positive electrode material, positive electrode material and lithium ion battery
CN109346708B (en) * 2018-11-20 2022-02-18 贵州大学 Preparation method of battery-grade carbon-coated ferrous phosphate

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CN1564343A (en) * 2004-03-25 2005-01-12 浙江大学 Method of preparing positive electrode composite material of Lithium ion cell contg, ferrous phosphate lithium salt-carbon
CN1649189A (en) * 2004-12-29 2005-08-03 浙江大学 Method for preparing carbon coated lithium ferrous phosphate composite material including metal conductive agent

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CN1401559A (en) * 2002-10-18 2003-03-12 北大先行科技产业有限公司 Method for preparing ferrous lithium phosphate, and lithium ion cell therewith
CN1564343A (en) * 2004-03-25 2005-01-12 浙江大学 Method of preparing positive electrode composite material of Lithium ion cell contg, ferrous phosphate lithium salt-carbon
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CN102709558B (en) * 2012-06-08 2014-04-09 中南大学 Method for preparing lithium iron phosphate from vivianite

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