CN103187567A - Preparation method of anode material lithium iron (II) phosphate for lithium ion cell - Google Patents

Preparation method of anode material lithium iron (II) phosphate for lithium ion cell Download PDF

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CN103187567A
CN103187567A CN2011104599013A CN201110459901A CN103187567A CN 103187567 A CN103187567 A CN 103187567A CN 2011104599013 A CN2011104599013 A CN 2011104599013A CN 201110459901 A CN201110459901 A CN 201110459901A CN 103187567 A CN103187567 A CN 103187567A
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lithium
iron
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presoma
phosphate
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CN103187567B (en
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张向军
顾远
卢世刚
阚素荣
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China Automotive Battery Research Institute Co Ltd
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Beijing General Research Institute for Non Ferrous Metals
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Abstract

The invention discloses a preparation method of anode material lithium iron (II) phosphate for a lithium ion cell. The preparation method mainly comprises the following two steps: (1) synthesis of precursor Li3Fe2(PO4)3, blending a lithium source, an iron source and a phosphorus source according to that the molar ratio of Li to Fe to P is 3:2:3, taking deionized water, absolute ethanol or acetone as a medium, ball-milling for 0.5-24 h, drying the obtained slurry, thermally treating for 3-24 hours at the temperature of 500-900 DEG C to obtain the precursor Li3Fe2(PO4)3; and (2) blending the obtained precursor Li3Fe2(PO4)3 and iron powder according to the molar ratio of 1:1, taking deionized water, absolute ethanol or acetone as the medium, ball-milling for 0.5-24 h, drying the obtained slurry, placing the dried slurry into a high-temperature furnace, under the atmosphere of inoxidizability, baking the dried slurry for 5-24 h at the temperature of 500-800 DEG C, and at last preparing the lithium iron (II) phosphate material. By adopting the principle that the lithium iron (II) phosphate material is synthesized by oxidation reduction between zero-valent iron and ferric iron source Li3Fe2(PO4)3 at high temperature, firstly, the pure phase Li3Fe2(PO4)3 intermediate is synthesized in advance, and then reacted with the zero-valent iron to synthesize the lithium iron (II) phosphate, so that the reaction process is easy to control. The synthesized product Li3Fe2(PO4)3 is high in chemical purity, good in electrochemical performance and high in batch stability.

Description

A kind of method for preparing 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 anode material for lithium ion battery LiFePO 4.
Background technology
Lithium ion battery has the energy density height, has extended cycle life, characteristics such as self discharge is little, memory-less effect, environmental friendliness, small-scale lithium ion cell occupies the monopoly status in information terminal product (mobile phone, portable computer, camcorder), its application has been extended to fields such as electric tool, LEV (Light Electric Vehicle), hybrid electric vehicle, telecommunications power backup, space from mobile phone, notebook at present, has broad application prospects.
LiFePO 4It is one of current anode material for lithium-ion batteries of being paid close attention to, have the thermal stability height, have extended cycle life, the inexpensive characteristics such as abundant, environmentally friendly of raw material, be very suitable for the battery applications field very responsive to fail safe, cycle life, power characteristic, use cost etc.Be that the lithium ion battery of positive electrode is because at the performance requirement that can satisfy present electric automobile development aspect safety, cost, life-span, the environmental protection with the ferrousphosphate lithium material, it is the preferred material of lithium-ion-power cell of new generation, become the competitively important directions of R and D of countries in the world, in recent years, because the quick progress of ferrousphosphate lithium material technology has obtained in electric tool, electric vehicle field widely applying.
The synthetic method of lithium iron phosphate cathode material is a lot, comprise that mainly carbothermic method, high temperature solid-state method are (for being different from carbothermic method, it is iron material prepares LiFePO 4 by high-temperature heat treatment method that the high temperature solid-state method at this place refers in particular to the divalent iron salt), microwave process for synthesizing, sol-gal process, molten salt growth method etc., wherein high temperature solid-state method, carbothermic method are the main method of present ferrousphosphate lithium material industrial-scale production.
High temperature solid-state method is to be precursor with ferrous compound such as ferric oxalate, and being material system with lithium salts such as lithium carbonate, phosphorus source such as ammonium dihydrogen phosphate prepares the method for LiFePO 4 by high-temperature heat treatment, and the valence state of iron is constant in the course of reaction, is divalent.As patent US6,514,640 have announced ferrousphosphate lithium material and preparation method thereof first, adopt the Li that presses stoichiometric 2CO 3(or LiOH), Fe(CH 2COOH) 2, NH 4H 2PO 4For raw material under inert atmosphere, at first be heated to 300-350 ℃ and remove NH 3, H 2O, CO 2, then be incubated 24 hours synthetic LiFePO 4s that obtain down at 800 ℃.
Carbothermic method is to be precursor with ferric iron such as iron oxide, ferric phosphate, with lithium salts, phosphorus source be material system, in the method that carbothermic method under the high temperature prepares LiFePO 4 of passing through under the participation of carbon, the valence state of iron is reduced to divalent by 3 valencys in the course of reaction.Announced first that as US 6528033 carbon thermal reduction prepares ferrousphosphate lithium material and material modified method thereof, adopting di-iron trioxide, ferric phosphate or tri-iron tetroxide is the raw material of iron, mix the method for high-temperature process synthesizing lithium ferrous phosphate under the inert atmosphere with lithium salts, phosphorus source and carbon.
In actual building-up process, often find, reaction system with ferric phosphate, lithium carbonate, organic carbon source such as sucrose is example, at high temperature carbothermic method prepares in the LiFePO 4 process, can find (accompanying drawing 1) by the powder x-ray diffraction methods analyst, about 450 ℃, the ferrous phosphate lithium grain begins to form, but has Li simultaneously 3Fe 2(PO 4) 3Deng the difraction spectrum of material, show in the LiFePO 4 forming process, to exist to generate Li 3Fe 2(PO 4) 3Side reaction or competitive reaction; Further improve reaction temperature and prolong temperature retention time, Li 3Fe 2(PO 4) 3Crystal can further react with iron containing compounds, and diffraction maximum will weaken gradually, but finally often more or less has the dephasign of ferriferous oxide, phosphoric acid lithium salts etc.Document (Feng Yu, Jingjie Zhanga, Reaction mechanism and electrochemical performance of LiFePO 4/ C cathode materials synthesized by carbothermal method[J] .Electrochimica Acta.2009) to the analysis of the reaction mechanism mechanism of reaction in the ferrousphosphate lithium material building-up process, also proved this point, because the existence of side reaction or competitive reaction, course of reaction is difficult to control when making synthesizing lithium iron phosphate materials, batch poor stability, product exists impurity or dephasign, reduces the chemical property of material.
PCT/US/9706671 has disclosed Li 3Fe 2(PO 4) 3Be a kind of doff lithium compound, but lower (the 2.8v vs Li of its discharge platform +/ Li), the low about 100～120mAh/g of specific capacity is difficult to obtain practical application in the secondary lithium battery that high specific energy requires.The present invention will be with Li 3Fe 2(PO 4) 3Be the intermediate product of preparation LiFePO 4, the redox reaction by itself and fe prepares LiFePO 4.
Summary of the invention
The purpose of this invention is to provide a kind of novel method for preparing lithium ferrous phosphate as anode material of lithium ion battery, its course of reaction is easy to control, the product LiFePO that is synthesized 4The chemical purity height, chemical property is good, batch stability is high.
To achieve these goals, the present invention takes following technical scheme:
At first synthetic presoma Li 3Fe 2(PO 4) 3, again with iron powder 1:1 batching in molar ratio, by the two redox reaction synthesizing lithium ferrous phosphate under non-oxidizing atmosphere medium and high temperature condition.Comprise the steps:
(1) presoma Li 3Fe 2(PO 4) 3Synthetic, Li source compound, source of iron, P source compound are Li:Fe:P=3:2:3 batching in molar ratio, are medium ball milling 0.5-24h with deionized water, absolute ethyl alcohol or acetone, behind the gained slurry drying, oxidizing atmosphere is following heat treatment 3-24 hour in 500-900 ℃, obtains presoma Li 3Fe 2(PO 4) 3
(2) resulting presoma Li 3Fe 2(PO 4) 3Being 1:1 batching in molar ratio with iron powder, is medium ball milling 0.5-24h with deionized water, absolute ethyl alcohol or acetone, behind the gained slurry drying, put into high temperature furnace, in non-oxidizing atmosphere, 500-800 ℃ following roasting 5-24 hour, make ferrousphosphate lithium material.
Described Li source compound is lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate, or lithium dihydrogen phosphate.
Described source of iron is iron powder, divalence or ferric oxide (preferred FeO, FeOOH, Fe 2O 3, Fe 3O 4), divalence or ferric nitrate (Fe (NO 3) 2, Fe (NO 3) 3), divalence or ferric acylate (preferred ferric acetate, ferrous acetate, ferric oxalate and ferrous oxalate).
Described P source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate.
Described ball-milling medium is deionized water, absolute ethyl alcohol or acetone.
Described drying mode can be spray drying, vacuumize.
Described oxidizing atmosphere is that air, oxygen concentration are the mist of 21%-100%.
Described nonoxidizing atmosphere be at least a in nitrogen and the argon gas, also can be reducing atmosphere.
In step 1, synthetic presoma Li 3Fe 2(PO 4) 3In, the stoichiometry in lithium source, source of iron, phosphorus source is the Li:Fe:P=3:2:3 batching in molar ratio.
In step 2, in the synthesizing lithium ferrous phosphate, Li 3Fe 2PO 3With the stoichiometry of iron powder be the 1:1 batching by the material mol ratio.
Advantage of the present invention is:
The purpose of this invention is to provide a kind of novel method for preparing LiFePO 4, its basic thought is based on ferric iron source Li 3Fe 2(PO 4) 3And redox reaction at high temperature takes place between the fe obtain LiFePO 4, need not to add other reducing agent, the valence state of iron becomes divalent by 3 valencys and zeroth order by redox reaction in the course of reaction, is different from two patented methods the prior art from reaction principle.
Preparation process comprises two steps, and the first step is at first to synthesize presoma Li 3Fe 2(PO 4) 3Li source compound, source of iron, P source compound are Li:Fe:P=3:2:3 batching in molar ratio, are medium ball milling 0.5-24h with deionized water, absolute ethyl alcohol or acetone, behind the gained slurry drying, at 500-900 ℃ of following heat treatment 3-24 hour, obtain presoma Li 3Fe 2(PO 4) 3Second step was with resulting presoma Li 3Fe 2(PO 4) 3Being 1:1 batching in molar ratio with iron powder, is medium ball milling 0.5-24h with deionized water, absolute ethyl alcohol or acetone, behind the gained slurry drying, put into high temperature furnace, in non-oxidizing atmosphere, 500-800 ℃ following roasting 5-24 hour, make ferrousphosphate lithium material.
Another characteristics of the present invention are Li 3Fe 2(PO 4) 3Synthetic can in oxidation or air atmosphere, carrying out, course of reaction is easy to control, is convenient to obtain chemical purity height, persursor material that crystal structure is complete; Again by the second step process, with Li 3Fe 2(PO 4) 3Mix with iron powder by material mol ratio 1:1 and to carry out high-temperature process, be easy to control chemical constituent and the phase composition of the LiFePO 4 that is synthesized, avoid occurring single step reaction synthetic in reaction not exclusively, the unmanageable problem of product dephasign.
For further improving the electric conductivity of ferrousphosphate lithium material, can add a spot of carbon forming agent and maybe synthetic ferrousphosphate lithium material be mixed with the even ball milling of small amount of carbon material in step 2, its purpose only limits to improve the electronic conduction ability of ferrousphosphate lithium material.
Description of drawings
Accompanying drawing 1 is the alternating temperature XRD test spectrogram of LiFePO 4 building-up process;
Accompanying drawing 2 is XRD temperature variation testing spectrograms of 400 ℃, 450 ℃, 500 ℃ temperature ranges, and wherein illustration is the amplification to the temperature variation testing spectrogram in angle of diffraction 20-40 degree interval;
Accompanying drawing 3 is the Li that make according to the inventive method embodiment 1 3Fe 2(PO 4) 3XRD spectra;
Accompanying drawing 4 is XRD spectra of the ferrousphosphate lithium material that makes according to the inventive method embodiment 1;
Accompanying drawing 5 is the ferrousphosphate lithium materials that make according to the inventive method embodiment 1.
Embodiment
Below in conjunction with case study on implementation and accompanying drawing the present invention is further detailed:
Accompanying drawing 1 is the alternating temperature XRD test spectrogram of LiFePO 4 building-up process, accompanying drawing 2 is the XRD temperature variation testing spectrograms in angle of diffraction 20-40 degree interval under 400 ℃, 450 ℃, the 500 ℃ temperature, by among attached Fig. 1 and 2 as can be seen, in 450 ℃ of-500 ℃ of temperature ranges, LiFePO has appearred in the XRD spectra generation significant change of reaction system in the time of 500 ℃ 4And Li 3Fe 2(PO 4) 3, Fe 2O 3Diffraction maximum.Show LiFePO 4Crystal generates temperature about about 500 ℃; Be accompanied by the carbothermic reduction reaction that generates LiFePO4, exist simultaneously to generate Li 3Fe 2(PO 4) 3Side reaction.Along with the rising of reaction temperature, Li 3Fe 2(PO 4) 3And Fe 2O 3Diffraction maximum die down LiFePO gradually 4Crystal is regular and growth gradually, and Li is described 3Fe 2(PO 4) 3And Fe 2O 3Can further reduce and generate LiFePO 4, but end product still exists a certain amount of impurity or dephasign, as a small amount of Li 3PO 4And Fe 2O 3Diffraction maximum Deng dephasign.Show the existence owing to side reaction or competitive reaction, course of reaction is difficult to control when making synthesizing lithium ferrous phosphate, and product exists impurity or dephasign, will directly influence the chemical property of material.
Embodiment 1
With lithium carbonate, di-iron trioxide and ammonium dihydrogen phosphate are according to Li:Fe:P mol ratio 3:2:3 batching, and ball milling obtained slurry after 100 minutes in ethanol medium; Above-mentioned slurry is carried out vacuumize obtain presoma, insert roasting in the Muffle furnace after presoma is adorned alms bowl, programming rate is 5 ℃/min, and 700 ℃ of insulation 5h cool to room temperature with the furnace, obtain Li 3Fe 2(PO 4) 3Presoma;
With Li 3Fe 2(PO 4) 3Presoma and iron powder are according to the 1:1 mol ratio, and ball milling obtained slurry after 30 minutes in ethanol medium; Above-mentioned slurry is carried out vacuumize obtain presoma, at nitrogen protection vacuum well type kiln roasting, programming rate is 5 ℃/min with presoma, and 600 ℃ of insulation 5h cool to room temperature with the furnace, obtain ferrousphosphate lithium material.
The assembling simulated battery is to the LiFePO of above-mentioned preparation 4Positive electrode carries out electrochemical property test.Be plus plate current-collecting body with the aluminium foil, wherein positive active material (is LiFePO 4), the mass ratio of acetylene black, Kynoar (PVDF) is 8:1:1, negative electricity is metal lithium sheet very, barrier film is import Celgard-2300,1mol/L LiPF 6The mixed solution of/ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1: 1: 1) is electrolyte.Being assemblied in the glove box of battery carried out, and the voltage range of constant current charge-discharge test is 2.5～4.2V.The system that discharges and recharges is according to the theoretical capacity calculating of 170mAh/g, and namely 1C is 170mA/g.Recording its 0.05C specific capacity is 133mAh/g.
The Li that accompanying drawing 3 makes according to the inventive method embodiment 1 3Fe 2(PO 4) 3XRD spectra; As seen from Figure 1, the prepared Li of the present invention 3Fe 2(PO 4) 3The xrd spectrogram of material and monoclinic system Li 3Fe 2(PO 4) 3Standard spectrogram unanimity (pdf#47-0107), belong to P21/n(14) space group, do not find the diffraction maximum of other dephasigns to show prepared Li 3Fe 2(PO 4) 3Material is pure phase.
Accompanying drawing 4 is XRD spectra of the ferrousphosphate lithium material that makes according to the inventive method embodiment 1, and all diffraction maximums all can index turn to the LiFePO of olivine structural 4, belong to the Pnma space group, do not find the diffraction maximum of other dephasigns, show prepared LiFePO 4Material is pure phase.
Accompanying drawing 5 is the ferrousphosphate lithium materials that make according to the inventive method embodiment 1, assembling button cell (negative pole is the lithium sheet), the discharge curve under the 0.05C multiplying power.Recording its 0.05C specific capacity is 133mAh/g, the high 8mAh/g of specific capacity (125 mAh/g) of the ferrous lithium of pure phosphoric acid (PCT/US/9706671) of more conventional high temperature solid-state method preparation.
Embodiment 2
With lithium hydroxide, ferric nitrate and diammonium hydrogen phosphate are according to Li:Fe:P mol ratio 3:2:3 batching, and ball milling obtained slurry after 12 hours in medium-acetone; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is adorned alms bowl insert roasting in the Muffle furnace, programming rate is 5 ℃/min, and 900 ℃ of insulation 3h cool to room temperature with the furnace, obtain Li 3Fe 2(PO 4) 3Presoma;
With Li 3Fe 2(PO 4) 3Presoma and iron powder are according to the 1:1 mol ratio, and ball milling obtained slurry after 12 hours in aqueous medium; Above-mentioned slurry is carried out spray drying obtain presoma, being that the mixed atmosphere of 5% nitrogen and hydrogen is mid-with presoma at hydrogen content goes into roasting in the pit-type furnace, and programming rate is 5 ℃/min, 600 ℃ of insulation 10h, cool to room temperature with the furnace, obtain ferrousphosphate lithium material.
The assembling simulated battery is to the LiFePO of above-mentioned preparation 4Positive electrode carries out electrochemical property test.Be plus plate current-collecting body with the aluminium foil, wherein positive active material (is LiFePO 4), the mass ratio of acetylene black, Kynoar (PVDF) is 8:1:1, negative electricity is metal lithium sheet very, barrier film is import Celgard-2300,1mol/L LiPF 6The mixed solution of/ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1: 1: 1) is electrolyte.Being assemblied in the glove box of battery carried out, and the voltage range of constant current charge-discharge test is 2.5～4.2V.The system that discharges and recharges is according to the theoretical capacity calculating of 170mAh/g, and namely 1C is 170mA/g.Recording its 0.05C specific capacity is 1300mAh/g.
Embodiment 3
Ferric oxalate and lithium dihydrogen phosphate are prepared burden according to Li:Fe:P mol ratio 3:2:3, and ball milling obtained slurry after 24 hours in ethanol medium; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is adorned alms bowl insert roasting in the Muffle furnace, programming rate is 5 ℃/min, and 800 ℃ of insulation 15h cool to room temperature with the furnace, obtain Li 3Fe 2(PO 4) 3Presoma;
With Li 3Fe 2(PO 4) 3Presoma and iron powder are according to the 1:1 mol ratio, and ball milling obtained slurry after 24 hours in medium-acetone; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is inserted roasting in the pit-type furnace in nitrogen atmosphere, programming rate is 5 ℃/min, and 800 ℃ of insulation 5h cool to room temperature with the furnace, obtain ferrousphosphate lithium material.
The assembling simulated battery is to the LiFePO of above-mentioned preparation 4Positive electrode carries out electrochemical property test.Be plus plate current-collecting body with the aluminium foil, wherein positive active material (is LiFePO 4), the mass ratio of acetylene black, Kynoar (PVDF) is 8:1:1, negative electricity is metal lithium sheet very, barrier film is import Celgard-2300,1mol/L LiPF 6The mixed solution of/ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1: 1: 1) is electrolyte.Being assemblied in the glove box of battery carried out, and the voltage range of constant current charge-discharge test is 2.5～4.2V.The system that discharges and recharges is according to the theoretical capacity calculating of 170mAh/g, and namely 1C is 170mA/g.Recording its 0.05C specific capacity is 129mAh/g.
Embodiment 4
According to Li:Fe:P mol ratio 3:2:3 batching, ball milling obtained slurry after 12 hours in ethanol medium with lithium acetate, iron powder and diammonium hydrogen phosphate; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is adorned alms bowl insert roasting in the Muffle furnace, programming rate is 5 ℃/min, and 600 ℃ of insulation 24h cool to room temperature with the furnace, obtain Li 3Fe 2(PO 4) 3Presoma;
With Li 3Fe 2(PO 4) 3Presoma and iron powder are according to the 1:1 mol ratio, and ball milling obtained slurry after 12 hours in aqueous medium; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is inserted roasting in the pit-type furnace in nitrogen atmosphere, programming rate is 5 ℃/min, and 650 ℃ of insulation 10h cool to room temperature with the furnace, obtain ferrousphosphate lithium material.
The assembling simulated battery is to the LiFePO of above-mentioned preparation 4Positive electrode carries out electrochemical property test.Be plus plate current-collecting body with the aluminium foil, wherein positive active material (is LiFePO 4), the mass ratio of acetylene black, Kynoar (PVDF) is 8:1:1, negative electricity is metal lithium sheet very, barrier film is import Celgard-2300,1mol/L LiPF 6The mixed solution of/ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1: 1: 1) is electrolyte.Being assemblied in the glove box of battery carried out, and the voltage range of constant current charge-discharge test is 2.5～4.2V.The system that discharges and recharges is according to the theoretical capacity calculating of 170mAh/g, and namely 1C is 170mA/g.Recording its 0.05C specific capacity is 135mAh/g.
Embodiment 5
According to Li:Fe:P mol ratio 3:2:3 batching, ball milling obtained slurry after 12 hours in aqueous medium with lithium oxalate, ferrous oxide and diammonium hydrogen phosphate; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is adorned alms bowl insert roasting in the Muffle furnace, programming rate is 10 ℃/min, and 800 ℃ of insulation 10h cool to room temperature with the furnace, obtain Li 3Fe 2(PO 4) 3Presoma;
With Li 3Fe 2(PO 4) 3Presoma and iron powder are according to the 1:1 mol ratio, and ball milling obtained slurry after 12 hours in ethanol medium; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is inserted roasting in the pit-type furnace in nitrogen atmosphere, programming rate is 8 ℃/min, and 750 ℃ of insulation 10h cool to room temperature with the furnace, obtain ferrousphosphate lithium material.
The assembling simulated battery is to the LiFePO of above-mentioned preparation 4Positive electrode carries out electrochemical property test.Be plus plate current-collecting body with the aluminium foil, wherein positive active material (is LiFePO 4), the mass ratio of acetylene black, Kynoar (PVDF) is 8:1:1, negative electricity is metal lithium sheet very, barrier film is import Celgard-2300,1mol/L LiPF 6The mixed solution of/ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1: 1: 1) is electrolyte.Being assemblied in the glove box of battery carried out, and the voltage range of constant current charge-discharge test is 2.5～4.2V.The system that discharges and recharges is according to the theoretical capacity calculating of 170mAh/g, and namely 1C is 170mA/g.Recording its 0.05C specific capacity is 134mAh/g.
Embodiment 6
According to Li:Fe:P mol ratio 3:2:3 batching, ball milling obtained slurry after 30 minutes in medium-acetone with lithium carbonate, ferrous acetate and diammonium hydrogen phosphate; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is adorned alms bowl insert roasting in the Muffle furnace, programming rate is 10 ℃/min, and 800 ℃ of insulation 15h cool to room temperature with the furnace, obtain Li 3Fe 2(PO 4) 3Presoma;
With Li 3Fe 2(PO 4) 3Presoma and iron powder are according to the 1:1 mol ratio, and ball milling obtained slurry after 12 hours in ethanol medium; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is inserted roasting in the pit-type furnace in nitrogen atmosphere, programming rate is 8 ℃/min, and 750 ℃ of insulation 10h cool to room temperature with the furnace, obtain ferrousphosphate lithium material.
The assembling simulated battery is to the LiFePO of above-mentioned preparation 4Positive electrode carries out electrochemical property test.Be plus plate current-collecting body with the aluminium foil, wherein positive active material (is LiFePO 4), the mass ratio of acetylene black, Kynoar (PVDF) is 8:1:1, negative electricity is metal lithium sheet very, barrier film is import Celgard-2300,1mol/L LiPF 6The mixed solution of/ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1: 1: 1) is electrolyte.Being assemblied in the glove box of battery carried out, and the voltage range of constant current charge-discharge test is 2.5～4.2V.The system that discharges and recharges is according to the theoretical capacity calculating of 170mAh/g, and namely 1C is 170mA/g.Recording its 0.05C specific capacity is 133mAh/g.
Embodiment 7
According to Li:Fe:P mol ratio 3:2:3 batching, ball milling obtained slurry after 10 hours in aqueous medium with lithium carbonate, FeOOH and diammonium hydrogen phosphate; Above-mentioned slurry is carried out vacuumize obtain presoma, presoma is adorned alms bowl insert roasting in the Muffle furnace, programming rate is 10 ℃/min, and 500 ℃ of insulation 24h cool to room temperature with the furnace, obtain Li 3Fe 2(PO 4) 3Presoma;
With Li 3Fe 2(PO 4) 3Presoma and iron powder are according to the 1:1 mol ratio, and ball milling obtained slurry after 20 hours in ethanol medium; Above-mentioned slurry is carried out spray drying obtain presoma, presoma is inserted roasting in the pit-type furnace in argon gas atmosphere, programming rate is 8 ℃/min, and 500 ℃ of insulation 24h cool to room temperature with the furnace, obtain ferrousphosphate lithium material.
The assembling simulated battery is to the LiFePO of above-mentioned preparation 4Positive electrode carries out electrochemical property test.Be plus plate current-collecting body with the aluminium foil, wherein positive active material (is LiFePO 4), the mass ratio of acetylene black, Kynoar (PVDF) is 8:1:1, negative electricity is metal lithium sheet very, barrier film is import Celgard-2300,1mol/L LiPF 6The mixed solution of/ethylene carbonate (EC)+diethyl carbonate (DEC)+dimethyl carbonate (DMC) (volume ratio 1: 1: 1) is electrolyte.Being assemblied in the glove box of battery carried out, and the voltage range of constant current charge-discharge test is 2.5～4.2V.The system that discharges and recharges is according to the theoretical capacity calculating of 170mAh/g, and namely 1C is 170mA/g.Recording its 0.05C specific capacity is 131mAh/g.

Claims (8)

1. the preparation method of an anode material for lithium ion battery LiFePO 4 is characterized in that, comprises the steps:
(1) presoma Li 3Fe 2(PO 4) 3Synthetic, Li source compound, source of iron, P source compound are the Li:Fe:P=3:2:3 batching in molar ratio, be medium ball milling 0.5-24h with deionized water, absolute ethyl alcohol or acetone, behind the gained slurry drying, oxidizing atmosphere is following heat treatment 3-24 hour in 500-900 ℃ of temperature, obtains presoma Li 3Fe 2(PO 4) 3
(2) resulting presoma Li 3Fe 2(PO 4) 3Being 1:1 batching in molar ratio with iron powder, is medium ball milling 0.5-24h with deionized water, absolute ethyl alcohol or acetone, behind the gained slurry drying, put into high temperature furnace, in non-oxidizing atmosphere, 500-800 ℃ following roasting 5-24 hour, make ferrousphosphate lithium material.
2. preparation method as claimed in claim 1, it is characterized in that: described Li source compound is lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate, or lithium dihydrogen phosphate.
3. preparation method as claimed in claim 1, it is characterized in that: described source of iron is iron powder, divalence or ferric oxide, ferrous nitrate, ferric nitrate or divalence or ferric acylate.
4. preparation method as claimed in claim 3, it is characterized in that: described divalence or ferric oxide are FeO, FeOOH, Fe 2O 3Or Fe 3O 4
5. preparation method as claimed in claim 3, it is characterized in that: described divalence or ferric acylate are ferric acetate, ferrous acetate, ferric oxalate or ferrous oxalate.
6. preparation method as claimed in claim 1, it is characterized in that: described P source compound is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium dihydrogen phosphate.
7. preparation method as claimed in claim 1, it is characterized in that: in described step (1) and step (2), drying mode is spray drying or vacuumize.
8. preparation method as claimed in claim 1, it is characterized in that: in described step (2), described nonoxidizing atmosphere is at least a in nitrogen and the argon gas, perhaps reducing atmosphere.
CN201110459901.3A 2011-12-31 2011-12-31 Preparation method of anode material lithium iron (II) phosphate for lithium ion cell Active CN103187567B (en)

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