CN101740776A - Preparation method of lithium ion battery anode material LiFePO4 - Google Patents

Preparation method of lithium ion battery anode material LiFePO4 Download PDF

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CN101740776A
CN101740776A CN200910254508A CN200910254508A CN101740776A CN 101740776 A CN101740776 A CN 101740776A CN 200910254508 A CN200910254508 A CN 200910254508A CN 200910254508 A CN200910254508 A CN 200910254508A CN 101740776 A CN101740776 A CN 101740776A
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lithium
preparation
anode material
ion batteries
lifepo
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王大伟
陶淳
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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 discloses a preparation method of lithium ion battery anode material LiFePO4. The preparation method is implemented by controlling uniformity of raw material granules, sieving by a sieve of 300-500 meshes to cause the granularity to be less than 50 mu m simultaneously; during sintering, controlling atmosphere condition and procedural temperature increase and decrease to control the product state of the reaction, sintering in over-dosed reducing atmosphere to reduce Fe3+ to Fe2+ and avoid formation of Fe3+ in LiFePO4 product as far as possible. The LiFePO4 prepared by the invention has more uniform granularity distribution and more regular appearance.

Description

A kind of anode material for lithium-ion batteries LiFePO 4The preparation method
Technical field
The invention belongs to the preparing technical field of inorganic material, relate to a kind of preparation of anode material for lithium-ion batteries, particularly a kind of anode material for lithium-ion batteries LiFePO 4The preparation method.
Background technology
Develop with LiCoO in 1991 from Japanese Sony company 2Be the commercial lithium battery of positive electrode, from then on lithium ion battery enters in notebook computer, digital camera, mobile communication equipment and the portable lighting apparatus.And lithium ion battery is memoryless with it, high-energy-density, high security, long life, wide operation temperature area and low contaminative and become the first-selected battery of power vehicle with battery.
Along with more and more serious environmental pollution problem in non-renewable flood tide consumption of human traditional energy and the use, the whole world is all very paid close attention to for the research and development and the popularization of electric motor car (EV) and oil and electricity hybrid vehicle (HEV), has all dropped into a large amount of research and development funds; The battery of the application requirements of electrokinetic cell exploitation has stable heat and chemical property, and more seems particularly crucial as the research and development of the power resources-lithium-ion-power cell of electric motor car.
Lithium ion battery basic composition is positive electrode, negative material, barrier film and electrolyte, wherein positive electrode is the core of lithium ion battery.Current, in the commercial lithium ion battery mainly with LiCoO 2Be positive electrode; This kind material has high gram volume (270mAh/g), but because its structural instability, when overcharging or during overdischarge, having excessive lithium ion and accumulate in negative pole, causes blast easily.
LiFePO 4Compare with other anode material of lithium battery, have best heat stability and chemical stability, i.e. its fail safe is the highest, so LiFePO 4Be best suited for being applied to the positive electrode of electrokinetic cell.LiFePO as anode material of lithium battery 4Preparation technology very crucial, preparation technology has determined the case of pattern, particle size and the ion of last moulding material.Present LiFePO 4Synthetic solid phase method, coprecipitation, hydrothermal synthesis method and spray pyrolysis arranged.Wherein high temperature solid-state method can obtain good crystallization LiFePO 4, can control LiFePO by the mechanochemistry method simultaneously 4Particle size and reunion degree.
Solid phase reaction is to prepare the more traditional method of inorganic material, generally includes repeatedly grinding and sintering.Usually preparation technology is: after raw mix is ground, at first 300-400 ℃ of Number of Decomposition hour to discharge gas, regrind then is again at 400-800 ℃ of sintering 10-24h; Before regrind, the compound of some carbon containings (as carboxylic acid) is added in the presoma, and purpose is to obtain LiFePO 4/ C composite material.The purity that solid phase method prepares material depends on the selection and the proportioning of raw material, the temperature and time of sintering, and the factors such as time of placing in air.Preparation LiFePO 4Solid phase reaction in Fe derive from ferric acetate or ferric oxalate, Li derives from lithium carbonate or lithium hydroxide, PO 4 3-Derive from ammonium hydrogen phosphate or ammonium phosphate.
LiFePO 4Preparation technology in the middle of difficult point be mainly derived from Fe and be oxidized to Fe easily 3-, so general protective atmosphere (Ar or the N that adopts inertia in the sintering process 2) or the atmosphere of weak reduction.Even but, Fe is arranged still at the atmosphere protection state 2O 3And Li 3Fe 2(PO 4) 3Form, especially when sintering temperature is higher than 800 ℃, Fe 2+Easier being oxidized to+3 valencys.Fe is oxidized to+and the reason of 3 valencys mainly is to be hidden in oxygen in the feed particles or the oxygen in the inert atmosphere.
Summary of the invention
The problem that the present invention solves is to provide a kind of anode material for lithium-ion batteries LiFePO 4The preparation method, by controlling uniform mixed material, the heating and cooling program of controlling sintering is accurately controlled the product state of reaction, avoids LiFePO as far as possible 4Fe in the middle of the product 3+Formation.
The present invention is achieved through the following technical solutions:
A kind of anode material for lithium-ion batteries LiFePO 4The preparation method, may further comprise the steps:
1) will be used to prepare LiFePO respectively 4Iron containing compounds, lithium-containing compound and contain PO 4 3-Phosphate, and molecular weight is that 700～1500 polyvinyl alcohol or molecular weight are mistake 300～500 mesh sieves of 10000～100000 polyaniline; After sieving, be iron containing compounds in molar ratio: lithium-containing compound: contain PO 4 3-Phosphate: polyvinyl alcohol or polyaniline=1: 1: 1: 0.01 ratio is fully mixed four kinds of compounds:
2) the gained mixture is carried out sintering under the protective atmosphere condition of hydrogen, presses following temperature programming and cooling:
Programming rate with 1～5 ℃/min is raised to 260～300 ℃ from room temperature, keeps 3～5h;
Be raised to 650～700 ℃ with 1～3 ℃/min then, keep 10～16h;
Cooling rate with 4～7 ℃/min drops to room temperature again;
3) product of sintering gained is disperseed and grind, obtain anode material for lithium-ion batteries LiFePO 4
Described iron containing compounds is Fe (OH) 3, Fe 2O 3, FeSO 47H 2O, Fe (NO 3) 39H 2O, FeCl 3, FeC 2O 4NH 2O, Fe 3(PO 4) 2NH 2O or FeO.
Described lithium-containing compound is Li 2CO 3, LiNO 3, LiOH, LiF, LiCl, LiBr, LiI or LiCH 2COOH2H 2O.
The described PO that contains 4 3-Phosphate be NH 4H 2PO 4Or (NH 4) 2HPO 4
The protective atmosphere of described hydrogen is dry N 2/ H 2Mist is counted N by volume 2: H 2=9～3: 1, whole process sintering keeps excess air.
The protective atmosphere of described hydrogen is dry Ar/H 2Mist is counted Ar: H by volume 2=9～3: 1, whole process sintering keeps excess air.
Described raw material iron containing compounds, lithium-containing compound and contain PO 4 3-Phosphate, and polyethylene is all crossed identical purpose sieve.
The abundant mixing of described raw material is fully to mix 10～25h in mixing bottle machine or ball mill.
Described dispersion and grinding are at the barreling 5～10h in bottle machine that rolls with polyurethane or polyvinyl chloride material.
Compared with prior art, the present invention has following beneficial technical effects:
The present invention crosses 300～500 mesh sieves by the uniformity of control feed particles, makes its granularity simultaneously less than 50 μ m; When carrying out sintering, control the product state of reaction by controlled atmospher condition and procedural heating and cooling, sintering makes Fe in excessive reducing atmosphere 3+Be reduced to Fe 2+, avoid LiFePO as far as possible 4Fe in the middle of the product 3+Formation.
The anode material for lithium-ion batteries LiFePO of the present invention's preparation 4The pattern homogeneous, the particle diameter rule; LiFePO with prior art for preparing 4Compare the LiFePO of the present invention's preparation 4More uniform particle size distribution and regular appearance are more arranged.
Description of drawings
Fig. 1 is the anode material for lithium-ion batteries LiFePO of the present invention's preparation 4X-ray diffraction spectrogram (XRD spectra); Abscissa is angle of diffraction 2 θ, and ordinate is relative diffracted intensity;
Fig. 2 is the anode material for lithium-ion batteries LiFePO of the present invention's preparation 4Low power sem photograph (SEM figure);
Fig. 3 is the sample of prior art for preparing and SEM (sem photograph) comparison diagram that the present invention prepares sample, and wherein scheming a is the sample of prior art for preparing, and figure b is the sample that the present invention prepares.
Embodiment
The present invention is by the uniform mixed material of control, and the heating and cooling program of controlling sintering is accurately controlled the product state of reaction, avoids LiFePO as far as possible 4Fe in the middle of the product 3+Formation.Below in conjunction with specific embodiment the present invention is done to describe in further detail, the explanation of the invention is not limited.
Embodiment 1
1) with 1mol LiOH, 1mol FeC 2O 42H 2O, 1mol NH 4H 2PO 4Cross 300 eye mesh screens respectively with 0.01mol polyvinyl alcohol (PVA, molecular weight are 700), then above-mentioned reactant is mixed, put into and roll bottle and roll a bottle machine, mixing 10h for what the polyvinyl chloride material was made;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace heat-agglomerating, be full of N in the body of heater 2/ H 2The gas of=3: 1 (volume ratio), whole process sintering keeps excess air, and promptly agglomerating chamber is a malleation;
Tube furnace is raised to 260 ℃ with the programming rate of 2 ℃/min from room temperature, keeps 3h;
Then the programming rate with 1 ℃/min is warmed up to 650 ℃, keeps 10h;
Cooling rate with 4 ℃/min drops to room temperature at last;
3) product of sintering gained is disperseed and grind, specifically adopt polyurethane to roll bottle and disperse 5h, promptly get anode material for lithium-ion batteries LiFePO 4
Embodiment 2
1) with 1mol LiOH, 1mol FeC 2O 42H 2O, 1mol NH 4H 2PO 4Cross 500 eye mesh screens respectively with 0.01mol polyvinyl alcohol (PVA, molecular weight are 1500), then above-mentioned reactant is mixed, put into bottle machine that rolls, mix 25h;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace and heat, be full of N in the body of heater 2/ H 2=9: 1 gas (volume ratio), whole process sintering keeps excess air;
Tube furnace is raised to 300 ℃ with the programming rate of 5 ℃/min from room temperature, keeps 5h;
Then the programming rate with 3 ℃/min is warmed up to 700 ℃, keeps 16h;
Cooling rate with 7 ℃/min drops to room temperature at last;
3) product with the sintering gained disperses, and specifically adopts polyurethane to roll bottle machine barreling and disperses 10h, promptly gets anode material for lithium-ion batteries LiFePO 4
Embodiment 3
1) with 1mol LiNO 3, 1mol Fe (OH) 3, 1mol (NH 4) 2HPO 4Cross 500 eye mesh screens respectively with 0.01mol polyaniline (molecular weight is 50000), then above-mentioned reactant is mixed, put into bottle machine that rolls, mix 18h;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace and heat, be full of N in the body of heater 2/ H 2The gas of=6: 1 (volume ratio), whole process sintering keeps excess air;
Tube furnace is raised to 260 ℃ with the programming rate of 1 ℃/min from room temperature, keeps 3h;
Then the programming rate with 1 ℃/min is warmed up to 700 ℃, keeps 10h;
Cooling rate with 4 ℃/min drops to room temperature at last;
3) product with the sintering gained disperses, and specifically adopts polyurethane to roll bottle machine barreling and disperses 8h, promptly gets anode material for lithium-ion batteries LiFePO 4
Embodiment 4
1) with 1mol LiCl, 1mol FeCl 3, 1mol (NH 4) 2HPO 4Cross 450 eye mesh screens respectively with 0.01mol polyvinyl alcohol (PVA, molecular weight are 10000), then above-mentioned reactant is mixed, put into bottle machine that rolls, mix 16h;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace and heat, be full of Ar/H in the body of heater 2The gas of=3: 1 (volume ratio), whole process sintering keeps excess air, and reducing atmosphere can be reduced into all+3 iron+2 iron in sintering process;
Tube furnace is raised to 280 ℃ with the programming rate of 2 ℃/min from room temperature, keeps 3h;
Then the programming rate with 2 ℃/min is warmed up to 680 ℃, keeps 15h;
Cooling rate with 5 ℃/min drops to room temperature at last;
3) product with the sintering gained disperses, and specifically adopts polyurethane to roll bottle machine barreling and disperses 8h, promptly gets anode material for lithium-ion batteries LiFePO 4
Embodiment 5
1) with 1mol LiF, 1mol FeSO 47H 2O, 1mol NH 4H 2PO 4Cross 500 eye mesh screens respectively with 0.01mol polyaniline (molecular weight is 1000), then above-mentioned reactant is mixed, put into polyurethane and roll a bottle machine, mix 18h;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace and heat, be full of N in the body of heater 2/ H 2The gas of=5: 1 (volume ratio), whole process sintering keeps excess air;
Tube furnace is raised to 275 ℃ with the programming rate of 4 ℃/min from room temperature, keeps 4h;
Then the programming rate with 3 ℃/min is warmed up to 680 ℃, keeps 16h;
Cooling rate with 6.5 ℃/min drops to room temperature at last;
3) product with the sintering gained disperses, and specifically adopts polyurethane to roll bottle machine barreling and disperses 10h, promptly gets anode material for lithium-ion batteries LiFePO 4
Embodiment 6
1) with 1mol LiBr, 1mol Fe (NO 3) 39H 2O, 1mol NH 4H 2PO 4Cross 350 eye mesh screens respectively with 0.01mol polyaniline (molecular weight 80000), then above-mentioned reactant is mixed, put into the polyurethane ball mill, mix 18h;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace and heat, be full of Ar/H in the body of heater 2The gas of=9: 1 (volume ratio), whole process sintering keeps excess air, and reducing atmosphere can be reduced into all+3 iron+2 iron in sintering process;
Tube furnace is raised to 280 ℃ with the programming rate of 5 ℃/min from room temperature, keeps 4h;
Then the programming rate with 3 ℃/min is warmed up to 650 ℃, keeps 10h;
Cooling rate with 6 ℃/min drops to room temperature at last;
3) product with the sintering gained disperses, and specifically adopts the polyvinyl chloride ball mill to disperse 9h, promptly gets anode material for lithium-ion batteries LiFePO 4
Embodiment 7
1) with 1mol LiCH 2COOH2H 2O, 1mol Fe 3(PO 4) 210H 2O, 1mol NH 4H 2PO 4Cross 450 eye mesh screens respectively with 0.01mol polyaniline (molecular weight 100000), then above-mentioned reactant is mixed, put into polyurethane ball milling bottle, mix 25h;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace and heat, be full of Ar/H in the body of heater 2The gas of=5: 1 (volume ratio);
Tube furnace is raised to 285 ℃ with the programming rate of 2.8 ℃/min from room temperature, keeps 3.5h;
Then the programming rate with 2 ℃/min is warmed up to 668 ℃, keeps 14h;
Cooling rate with 5.5 ℃/min drops to room temperature at last;
3) product with the sintering gained disperses, and specifically adopts polyvinyl chloride to roll bottle machine barreling and disperses 7h, promptly gets anode material for lithium-ion batteries LiFePO 4
Embodiment 8
1) with 1mol Li 2CO 3, 1mol Fe 2O 3, 1mol (NH 4) 2HPO 4Cross 400 eye mesh screens respectively with 0.01mol polyvinyl alcohol (molecular weight 800), then above-mentioned reactant is mixed, put into the polyvinyl chloride ball mill, mix 20h;
2) mixture of gained is put into silica crucible, then crucible is put into tube furnace and heat, be full of Ar/H in the body of heater 2The gas of=9: 1 (volume ratio);
Tube furnace is raised to 265 ℃ with the programming rate of 1.5 ℃/min from room temperature, keeps 5h;
Then the programming rate with 2.2 ℃/min is warmed up to 690 ℃, keeps 12h;
Cooling rate with 7 ℃/min drops to room temperature at last;
3) product with the sintering gained disperses, and specifically adopts polyvinyl chloride ball milling bottle to disperse 10h, promptly gets anode material for lithium-ion batteries LiFePO 4
Anode material for lithium-ion batteries LiFePO to the present invention's preparation 4Do following detection:
1, the anode material for lithium-ion batteries LiFePO of the present invention's preparation 4The X-ray diffraction spectrogram as shown in Figure 1, the LiFePO of the present invention preparation as can be seen 4Thing is mutually pure, and crystallization is complete;
2, the anode material for lithium-ion batteries LiFePO of the present invention's preparation 4The low power sem photograph as shown in Figure 2, the LiFePO of the present invention preparation as can be seen 4The pattern homogeneous, the particle diameter rule;
3, the anode material for lithium-ion batteries LiFePO of the present invention's preparation 4LiFePO with prior art for preparing 4Low power ESEM comparison diagram, wherein, figure a be the LiFePO of prior art for preparing 4, figure b is the LiFePO of the present invention's preparation 4Comparison diagram a and figure b be the LiFePO of the present invention's preparation as can be seen 4More uniform particle size distribution and regular appearance are more arranged.

Claims (9)

1. anode material for lithium-ion batteries LiFePO 4The preparation method, it is characterized in that, may further comprise the steps:
1) will be used to prepare LiFePO respectively 4Iron containing compounds, lithium-containing compound and contain PO 4 3-Phosphate, and molecular weight is that 700～1500 polyvinyl alcohol or molecular weight are mistake 300～500 mesh sieves of 10000～100000 polyaniline; After sieving, be iron containing compounds in molar ratio: lithium-containing compound: contain PO 4 3-Phosphate: polyvinyl alcohol or polyaniline=1: 1: 1: 0.01 ratio is fully mixed four kinds of compounds;
2) the gained mixture is carried out sintering under the protective atmosphere condition of hydrogen, presses following temperature programming and cooling:
Programming rate with 1～5 ℃/min is raised to 260～300 ℃ from room temperature, keeps 3～5h;
Be raised to 650～700 ℃ with 1～3 ℃/min then, keep 10～16h;
Cooling rate with 4～7 ℃/min drops to room temperature again;
3) product of sintering gained is disperseed and grind, obtain anode material for lithium-ion batteries LiFePO 4
2. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: described iron containing compounds is Fe (OH) 3, Fe 2O 3, FeSO 47H 2O, Fe (NO 3) 39H 2O, FeCl 3, FeC 2O 4NH 2O, Fe 3(PO 4) 2NH 2O or FeO.
3. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: described lithium-containing compound is Li 2CO 3, LiNO 3, LiOH, LiF, LiCl, LiBr, LiI or LiCH 2COOH2H 2O.
4. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: the described PO of containing 4 3-Phosphate be NH 4H 2PO 4Or (NH 4) 2HPO 4
5. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: the protective atmosphere of described hydrogen is dry N 2/ H 2Mist is counted N by volume 2: H 2=9～3: 1, whole process sintering keeps excess air.
6. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: the protective atmosphere of described hydrogen is dry Ar/H 2Mist is counted Ar: H by volume 2=9～3: 1, whole process sintering keeps excess air.
7. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: described raw material iron containing compounds, lithium-containing compound and contain PO 4 3-Phosphate, and polyethylene is all crossed identical purpose sieve.
8. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: described abundant mixing is fully to mix 10～25h in mixing bottle machine or ball mill.
9. anode material for lithium-ion batteries LiFePO as claimed in claim 1 4The preparation method, it is characterized in that: described dispersion and grinding are to roll the barreling 5～10h in bottle machine that rolls that bottle material is polyurethane or polyvinyl chloride.
CN200910254508A 2009-12-25 2009-12-25 Preparation method of lithium ion battery anode material LiFePO4 Pending CN101740776A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103208626A (en) * 2012-01-17 2013-07-17 深圳市沃特玛电池有限公司 Method for preparing lithium iron phosphate/carbon composite material by using aniline
US9073760B2 (en) 2010-12-24 2015-07-07 Shoei Chemical Inc. Manufacturing method and manufacturing device for multiple oxide

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9073760B2 (en) 2010-12-24 2015-07-07 Shoei Chemical Inc. Manufacturing method and manufacturing device for multiple oxide
CN103208626A (en) * 2012-01-17 2013-07-17 深圳市沃特玛电池有限公司 Method for preparing lithium iron phosphate/carbon composite material by using aniline
CN103208626B (en) * 2012-01-17 2016-03-02 深圳市沃特玛电池有限公司 A kind of method adopting aniline to prepare lithium iron phosphate/carbon composite material

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