CN102623705A - Lithium ion battery cathode material LiFePO4/C, and preparation method and application thereof - Google Patents

Lithium ion battery cathode material LiFePO4/C, and preparation method and application thereof Download PDF

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CN102623705A
CN102623705A CN2012100924119A CN201210092411A CN102623705A CN 102623705 A CN102623705 A CN 102623705A CN 2012100924119 A CN2012100924119 A CN 2012100924119A CN 201210092411 A CN201210092411 A CN 201210092411A CN 102623705 A CN102623705 A CN 102623705A
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lithium
preparation
anode material
ion batteries
batteries lifepo
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CN102623705B (en
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史雪锋
刘伟利
***
史顺君
陈鹏
陈永祥
许�鹏
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Yixing Xinchi Energy Technology Co., Ltd
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Sharp Point Of Jiangsu Speeds In Green Power Co Ltd
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Abstract

The invention discloses a preparation method for a lithium ion battery cathode material LiFePO4/C. The method comprises the following steps of: dissolving a lithium source, a ferric salt, phosphate and a citric acid into water, and performing uniform mixing to obtain a mixed solution; preserving the heat of the mixed solution for 6 to 12 hours at 160 to 200 DEG C, and cooling the mixed solution to obtain a precursor product; and adding glucose into the precursor product, stirring the mixture for 3 to 10 hours, filtering and drying the mixture, calcining the mixture for 8 to 12 hours at 600 to 700 DEG C under the protection of nitrogen and argon, and cooling the mixture to obtain the lithium ion battery cathode material LiFePO4/C. The invention also discloses the lithium ion battery cathode material LiFePO4/C, which consists of microspheres, wherein each microsphere has the diameter of 1 to 3 mu m, and is mesoporous. The material has high tap density and high specific capacity. The preparation method has the advantages of low cost of required raw materials, simplicity in preparation, high process controllability, low energy consumption and the like, and is suitable for large-scale production.

Description

A kind of anode material for lithium-ion batteries LiFePO 4/ C
Technical field
The present invention relates to anode material for lithium-ion batteries LiFePO 4/ C and preparation field thereof are specifically related to a kind of employing Hydrothermal Preparation mesoporous microsphere shape anode material for lithium-ion batteries LiFePO 4The anode material for lithium-ion batteries LiFePO of the method of/C and preparation thereof 4/ C and application.
Background technology
Present anode material for lithium-ion batteries LiFePO 4The chemical property of/C has obtained very big improvement, and the specific capacity under the low range has almost reached theoretical capacity, and its high-rate charge-discharge capability has also had very big improvement.But anode material for lithium-ion batteries LiFePO 4/ C still is faced with a technical problem, and that is exactly that its actual tap density is very low: LiFePO 4Theoretical tap density be 3.6g/cm 3Yet, present most of anode material for lithium-ion batteries LiFePO 4The actual tap density of/C has only 1～1.4g/cm 3
Carbon coats and the particle size nanometerization can be improved anode material for lithium-ion batteries LiFePO 4The high rate capability of/C, but the improvement of this performance is to be cost with the energy density of sacrificing battery.Under identical specific capacity prerequisite, the actual tap density that improves material can improve the energy density of battery.Usually, anode material for lithium-ion batteries LiFePO 4The particle size of/C is more little, and carbon content is many more, and its actual tap density is low more, has nano-sized particles and carbon and coats irregular anode material for lithium-ion batteries LiFePO 4The actual tap density of/C generally is not higher than 1.0g/cm 3Though mix through machinery and can improve anode material for lithium-ion batteries LiFePO 4The actual tap density of/C, but particle shaping complex technical process.Because it is easily low tightly packed to have the spheric granules of nominal particle size, therefore, the anode material for lithium-ion batteries LiFePO that constitutes by microsphere particle 4/ C has higher actual tap density than nano particle in irregular shape.
(H.M.Xie, R.S.Wang, R.J.Yang, L.Zhang.Optimized LiFePO such as Xie 4-polyacene cathode material for lithium-ion batteries.Advanced Materials, 2006,18:2609-2613.) LiFePO that coats with the synthetic carbon of the method for crystallization control is disclosed 4/ C microspheres with solid, the actual tap density of these microballoons is up to 1.6g/cm 3, and its specific discharge capacity when the 5C multiplying power is 97mAh/g.But compare the particle of nano-scale, this bulky grain microspheres with solid has very long electronics and ion transfer path, and electrolyte is difficult to be penetrated into the inside of bulky grain microspheres with solid and conductive carbon film can only be coated on LiFePO 4On the surface of/C microspheres with solid, limited LiFePO 4The further improvement of/C microspheres with solid chemical property.
Publication number is that the one Chinese patent application of CN 101299458A discloses a kind of raising anode material for lithium-ion batteries LiFePO 4The method of/C tap density is with FePO 4XH 2O and LiOHH 2O, Li 2CO 3Or CH 3COOLi2H 2O and polyethylene glycol mix, and add auxiliary agent, add entry furnishing rheology attitude, and then roasting obtain anode material for lithium-ion batteries LiFePO under inert atmosphere 4/ C.Though this technical scheme can be with anode material for lithium-ion batteries LiFePO 4The actual tap density of/C is from 0.77～0.79g/cm 3Bring up to 1.0～1.05g/cm 3, and have high-rate charge-discharge capability preferably, but this anode material for lithium-ion batteries LiFePO 4The actual tap density of/C needs further to improve.
Hydro thermal method is a synthetic tiny LiFePO 4The effective method of/C particle.Hydrothermal reaction at low temperature helps the control tested, but can cause LiFePO 4Thereby very poor its chemical property that influences of the degree of crystallinity of/C.
Publication number is that the one Chinese patent application of CN 101777637A discloses a kind of green LiFePO 4The preparation method of/C nano composite anode material takes by weighing a certain amount of ironic citrate, Li source compound, P source compound by certain mol proportion, and is dissolved in deionized water at a certain temperature and is made into certain density mixed liquor; Adopt certain drying mode to carry out drying then; Promptly obtain the presoma powder after the grinding, the presoma powder is put into sintering furnace, in inert atmosphere, carry out sintering; Naturally cool to room temperature then, promptly make LiFePO 4/ C nano composite anode material.Though it is this technical scheme obtains mixed liquor at 30 ℃～80 ℃, and carries out obtaining the presoma powder after the drying, similar with hydro thermal method; Can find out from electron microscope scanning figure; The particle diameter of its preparation is about 50nm, but its nano particle out-of-shape, green LiFePO 4The actual tap density of/C nano composite anode material is still lower.
Summary of the invention
The invention provides a kind of anode material for lithium-ion batteries LiFePO 4The preparation method of/C is a source of iron with the trivalent iron salt of cheapness, adopts Hydrothermal Preparation simple and easy to control to have the mesoporous microsphere shape anode material for lithium-ion batteries LiFePO of high-tap density 4/ C.
A kind of anode material for lithium-ion batteries LiFePO 4The preparation method of/C may further comprise the steps:
1) lithium source, trivalent iron salt, phosphate and citric acid is soluble in water separately or together, mix and obtain mixed liquor;
2) mixed liquor in the step 1) is sealed insulation 6h～12h in 160 ℃～200 ℃, obtain the presoma product after the cooling;
3) to step 2) in the presoma product in add the glucose account for presoma product total weight 3%～10%; Stir 3h～10h; Stir back filtration, drying, 600 ℃～700 ℃ calcining 8h～12h under nitrogen and argon shield obtain anode material for lithium-ion batteries LiFePO after the cooling again 4/ C.
The present invention behind 600 ℃～700 ℃ calcining 8h～12h, obtains the anode material for lithium-ion batteries LiFePO of excellent performance through sealing insulation 6h～12h in 160 ℃～200 ℃ and after adding glucose carbon source 4/ C.
In order better to be invented effect, below as of the present invention preferred:
Described lithium source is lithium acetate or lithium hydroxide, adopts lithium acetate, lithium hydroxide as the lithium source, because these two kinds of lithium sources are soluble in water and be alkalescence, can not stay foreign ion after scalable Property of Acid and Alkali of Solution and the process calcining.
Trivalent iron salt is with respect to divalent iron salt, and is more cheap, and divalent iron salt is very easily oxidized, and further preferred, described trivalent iron salt is Fe (NO 3) 39H 2O, nitrate ion in this trivalent iron salt and the ammonium radical ion in the phosphate can decompose after forming the ammonium nitrate calcining, thereby can not leave impurity.
Described phosphate is (NH 4) H 2PO 4Or (NH 4) 2HPO 4, compare phosphoric acid, these two kinds of phosphate are solid, the amount that takes by weighing when using is on the one hand controlled easily, and the ammonium radical ion in the phosphate can be combined into ammonium nitrate with the nitrate ion in the trivalent iron salt, helps to decompose.
The mol ratio of lithium source, trivalent iron salt, phosphate, citric acid is 1～1.1 in the described mixed liquor: 1: 1: 1～1.2, and the concentration of lithium source, trivalent iron salt, phosphate, citric acid is 0.3mol/L～0.5mol/L in the described mixed liquor.The control of material quantity and the control of material concentration are helped anode material for lithium-ion batteries LiFePO 4The amount of lithium, iron and phosphoric acid remains on most suitable scope among/the C, helps obtaining the anode material for lithium-ion batteries LiFePO of excellent performance 4/ C.
The mol ratio of described nitrogen and argon gas is 3: 7～27, and the total gas pressure of described nitrogen and argon gas is 5MPa～7MPa.The present invention adopts nitrogen and two kinds of gases of argon gas; The price of nitrogen is lower with respect to argon gas on the one hand, and is lower than simple use argon gas cost, on the other hand; The ratio and the total gas pressure of nitrogen and argon gas are limited to preferable range; A stable calcination environment is provided, in calcination process, has removed in the unstable impurity such as ammonium nitrate that generates in the preparation process, avoided the introducing of other impurity.
The present invention also provides a kind of anode material for lithium-ion batteries LiFePO of described preparation method's preparation 4/ C has mesoporous microsphere shape structure and has high-tap density.
Described anode material for lithium-ion batteries LiFePO 4/ C is made up of microballoon, and this diameter of micro ball is 1 μ m～3 μ m, and this microballoon is mesoporous shape.This mesoporous shape microballoon anode material for lithium-ion batteries LiFePO 4/ C is that a nano particle tight agglomeration becomes mesoporous shape microballoon, and this mesoporous shape microballoon can form three-dimensional electronic passage and ion channel, is anode material for lithium-ion batteries LiFePO 4/ C has the ideal structure of high-tap density and height ratio capacity.
Described anode material for lithium-ion batteries LiFePO 4The application of/C in preparation lithium ion battery positive electrode and lithium ion battery.
A kind of lithium ion battery positive electrode, process by following raw materials by weight percent:
Described anode material for lithium-ion batteries LiFePO 4/ C 16%～20%;
Conductive carbon black 0.8%～1.2%;
Polyvinylidene fluoride 0.6%～1%;
1-Methyl-2-Pyrrolidone 78%～82%.
Wherein, polyvinylidene fluoride can adopt the commercially available general trade mark.
The preparation method of described lithium ion battery positive electrode may further comprise the steps:
With anode material for lithium-ion batteries LiFePO 4/ C, conductive carbon black and polyvinylidene fluoride mix, and add the 1-Methyl-2-Pyrrolidone vacuum stirring again and process uniform slurry, then uniform slurry are coated on the aluminium foil with coating process, and oven dry is after compacting, branch cut into positive electrode.The positive electrode of preparation is used in the lithium ion battery, and this lithium ion battery has higher specific capacity.
Compared with prior art, the present invention has following advantage:
Anode material for lithium-ion batteries LiFePO of the present invention 4Among the preparation method of/C, as source of iron, adopt Hydrothermal Preparation simple and easy to control to go out anode material for lithium-ion batteries LiFePO with the trivalent iron salt of cheapness 4/ C in the incipient stage of hydro-thermal reaction, deposits owing to presoma solubility in the mixed liquor reduces to have the granular precursor of nano-scale; The nano particle of these dispersions (i.e. a nano particle, particle diameter is about 100nm) surface is unstable, for reducing interfacial tension; They are agglomerated into fine and close microballoon (secondary microballoon), and along with the prolongation of time, pressure increases under 160 ℃～200 ℃ high temperature; The secondary microballoon of these reunions can experience the process of one section dissolution-deposition; In this course, the microballoon of the densification that is agglomerated into is etched into meso-hole structure, and these mesoporous shape microballoon presomas form single-phase anode material for lithium-ion batteries LiFePO behind sintering 4/ C.The mesoporous shape microballoon of these hierarchical organizations can closely be piled up together, makes anode material for lithium-ion batteries LiFePO 4/ C has up to 1.5g/cm 3Tap density.
The anode material for lithium-ion batteries LiFePO of the present invention's preparation 4/ C is made up of microballoon, and this diameter of micro ball is 1 μ m～3 μ m, has high-tap density, and this microballoon is mesoporous shape, and the meso-hole structure on the microballoon helps electrolyte permeability to go into microballoon inside, and electrolyte is fully contacted with active material.Simultaneously, bigger specific area and the electronics of lacking and the conducting path of ion of nano particle, thus can improve its chemical property.Therefore, the anode material for lithium-ion batteries LiFePO of the present invention's preparation 4/ C possesses high-tap density simultaneously, and the lithium ion battery of this material preparation has height ratio capacity, and this material has excellent chemical property, has broad application prospects.
Anode material for lithium-ion batteries LiFePO of the present invention 4The lithium ion battery of/C preparation is 102mAh/g in 25 ℃ of following 20C multiplying power discharging specific capacities of room temperature; Can satisfy the requirement of power-type lithium ion battery; And preparation method of the present invention has, and the needed raw material cost is lower, the preparation method is simple, process is easy to control, low power consumption and other advantages, is suitable for large-scale production.
Description of drawings
Fig. 1 is the anode material for lithium-ion batteries LiFePO of embodiment 1 preparation 4The X-ray diffractogram of/C;
Fig. 2 is the anode material for lithium-ion batteries LiFePO of embodiment 1 preparation 4(100K doubly) stereoscan photograph of/C;
Fig. 3 is the anode material for lithium-ion batteries LiFePO of embodiment 1 preparation 4(20K doubly) stereoscan photograph of/C;
Fig. 4 is that the lithium ion battery of embodiment 1 preparation recycles the continuous specific capacity curve that charges and discharge circulation for 10 times of back test under different multiplying.
Embodiment
Below in conjunction with embodiment the present invention is done detailed explanation, following examples do not produce restriction to the present invention.
Embodiment 1
1) with LiOHH 2O, Fe (NO 3) 39H 2O, NH 4H 2PO 4And citric acid (citric acid) 1: 1: 1 in molar ratio: 1 takes by weighing raw material; Respectively it is dissolved in the deionized water; Obtain the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution respectively, wherein, the concentration of lithium hydroxide is 0.3mol/L in the aqueous solution of lithium source; The concentration of ferric nitrate is 0.3mol/L in the trivalent iron salt aqueous solution; The concentration of ammonium dihydrogen phosphate is 0.3mol/L in the aqueous phosphatic, and the concentration of citric acid is 0.3mol/L in the aqueous citric acid solution, the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume is mixed obtain mixed liquor again;
2) mixed liquor in the step 1) is poured in the autoclave, again autoclave is put into baking oven, sealing insulation 10h places cooling water with autoclave then in 180 ℃, obtains the presoma product after the cooling;
3) to step 2) in the presoma product add 5% glucose (as carbon source) with respect to presoma product total weight; Stir 5h, stir back centrifugal filtration, oven dry, again 650 ℃ of calcining 10h under nitrogen and argon shield; Wherein, The mol ratio of nitrogen and argon gas is 1: 9, and nitrogen and argon gas total gas pressure are 6MPa, obtain anode material for lithium-ion batteries LiFePO after the cooling 4/ C.
The anode material for lithium-ion batteries LiFePO that present embodiment obtains 4The X-ray diffractogram of/C is as shown in Figure 1, is pure LiFePO 4Phase, carbon is non crystalline structure.The anode material for lithium-ion batteries LiFePO that present embodiment obtains 4The stereoscan photograph of/C is like Fig. 2, shown in 3; Like Fig. 2, shown in 3, this anode material for lithium-ion batteries LiFePO 4/ C is made up of microballoon, and this diameter of micro ball is 1 μ m～3 μ m, and this microballoon is mesoporous shape, and the particle diameter of a nano particle is about 100nm.Record this anode material for lithium-ion batteries LiFePO 4Residual carbon weight percentage among the/C is 2.65%, and its actual tap density is 1.51g/cm 3
The anode material for lithium-ion batteries LiFePO that present embodiment is obtained 4/ C, conductive carbon black, polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd.; Model is FR901) mixed by weight 91: 5: 4; Obtain compound, process uniform slurry for the solvent vacuum stirring with 1-Methyl-2-Pyrrolidone (NMP, consumption are 4.12 times of compound weight); Be coated in uniform slurry on the aluminium foil of thickness 20 μ m with coating process then; Toast 12h down for 90 ℃ through baking oven, under roll squeezer, pole piece compacting, branch are cut into anode pole piece then, as positive electrode.As negative electrode, positive and negative electrode capacity ratio 1: 1.15 is assembled into lithium ion battery in being full of the glove box of argon gas with the pole piece of carbon coated material on the Copper Foil.Carry out charge-discharge test with constant current; Charging and discharging voltage is between 2.5～4.2V; Its specific capacity at 25 ℃ of following batteries first charge-discharge under (0.1C, 1C, 5C, 10C, 20C) different multiplying is as shown in table 1; Record 0.1C and discharge and recharge down first that reversible specific capacity is 155mAh/g, 1C first charge-discharge reversible specific capacity is 137mAh/g, and 5C first charge-discharge reversible specific capacity is 118mAh/g; 10C first charge-discharge reversible specific capacity is 109mAh/g, and 20C first charge-discharge reversible specific capacity is 102mAh/g.This lithium ion battery under different multiplying to recycle the continuous specific capacity curve that charges and discharge circulation for 10 times of back test as shown in Figure 4, each charges and discharge stable cycle performance through 10 times under many multiplying powers.
Table 1
Embodiment 2
1) with CH 3COOLi2H 2O, Fe (NO 3) 39H 2O, NH 4H 2PO 4And citric acid (citric acid) 1.05: 1: 1 in molar ratio: 1 takes by weighing raw material; Respectively it is dissolved in the deionized water; Obtain the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution respectively, wherein, the concentration of lithium acetate is 0.4mol/L in the aqueous solution of lithium source; The concentration of ferric nitrate is 0.4mol/L in the trivalent iron salt aqueous solution; The concentration of ammonium dihydrogen phosphate is 0.4mol/L in the aqueous phosphatic, and the concentration of citric acid is 0.4mol/L in the aqueous citric acid solution, the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume is mixed obtain mixed liquor again;
2) mixed liquor in the step 1) is poured in the autoclave, again autoclave is put into baking oven, sealing insulation 10h places cooling water with autoclave then in 180 ℃, obtains the presoma product after the cooling;
3) to step 2) in the presoma product add 5% glucose (as carbon source) with respect to presoma product total weight; Stir 5h, stir back centrifugal filtration, oven dry, again 650 ℃ of calcining 10h under nitrogen and argon shield; Wherein, The mol ratio of nitrogen and argon gas is 2: 8, and nitrogen and argon gas total gas pressure are 6MPa, obtain anode material for lithium-ion batteries LiFePO after the cooling 4/ C.
According to the X-ray diffraction map analysis, the anode material for lithium-ion batteries LiFePO that present embodiment obtains 4/ C is pure LiFePO 4Phase, carbon is non crystalline structure.Can know this anode material for lithium-ion batteries LiFePO according to stereoscan photograph 4/ C is made up of microballoon, and this diameter of micro ball is 1 μ m～3 μ m, and this microballoon is mesoporous shape.Record this anode material for lithium-ion batteries LiFePO 4Residual carbon weight percentage among the/C is 6.3%, and its actual tap density is 1.47g/cm 3
The anode material for lithium-ion batteries LiFePO that present embodiment is obtained 4/ C, conductive carbon black, polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd.; Model is FR901) mixed by weight 91: 5: 4; Obtain compound, process uniform slurry for the solvent vacuum stirring with 1-methyl-2 pyrrolidones (NMP, consumption are 4.12 times of compound weight); Be coated in uniform slurry on the aluminium foil of thickness 20 μ m with coating process then; Toast 12h down for 90 ℃ through baking oven, under roll squeezer, pole piece compacting, branch are cut into anode pole piece then, as positive electrode.As negative electrode, positive and negative electrode capacity ratio 1: 1.15 is assembled into lithium ion battery in being full of the glove box of argon gas with the pole piece of carbon coated material on the Copper Foil.Carry out charge-discharge test with constant current, charging and discharging voltage is between 2.5～4.2V, under 25 ℃, records 0.1C and discharges and recharges down first that reversible specific capacity is 145mAh/g, and 1C first charge-discharge reversible specific capacity is 127mAh/g, and good cycling stability.
Embodiment 3
1) with LiOHH 2O, Fe (NO 3) 39H 2O, NH 4H 2PO 4And citric acid (citric acid) 1: 1: 1 in molar ratio: 1 takes by weighing raw material; Respectively it is dissolved in the deionized water; Obtain the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution respectively, wherein, the concentration of lithium hydroxide is 0.5mol/L in the aqueous solution of lithium source; The concentration of ferric nitrate is 0.5mol/L in the trivalent iron salt aqueous solution; The concentration of ammonium dihydrogen phosphate is 0.5mol/L in the aqueous phosphatic, and the concentration of citric acid is 0.5mol/L in the aqueous citric acid solution, the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume is mixed obtain mixed liquor again; Again the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume are mixed and obtain mixed liquor;
2) mixed liquor in the step 1) is poured in the autoclave, again autoclave is put into baking oven, sealing insulation 12h places cooling water with autoclave then in 200 ℃, obtains the presoma product after the cooling;
3) to step 2) in the presoma product add 5% glucose (as carbon source) with respect to presoma product total weight; Stir 5h, stir back centrifugal filtration, oven dry, again 700 ℃ of calcining 12h under nitrogen and argon shield; Wherein, The mol ratio of nitrogen and argon gas is 3: 7, and nitrogen and argon gas total gas pressure are 6MPa, obtain anode material for lithium-ion batteries LiFePO after the cooling 4/ C.
According to the X-ray diffraction map analysis, the anode material for lithium-ion batteries LiFePO that present embodiment obtains 4/ C is pure LiFePO 4Phase, carbon is non crystalline structure.Can know this anode material for lithium-ion batteries LiFePO according to stereoscan photograph 4/ C is made up of microballoon, and this diameter of micro ball is 1 μ m～3 μ m, and this microballoon is mesoporous shape.Record this anode material for lithium-ion batteries LiFePO 4Residual carbon weight percentage among the/C is 1.7%, and its actual tap density is 1.54g/cm 3
The anode material for lithium-ion batteries LiFePO that present embodiment is obtained 4/ C, conductive carbon black, polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd.; Model is FR901) mixed by weight 91: 5: 4; Obtain compound, process uniform slurry for the solvent vacuum stirring with 1-methyl-2 pyrrolidones (NMP, consumption are 4.12 times of compound weight); Be coated in uniform slurry on the aluminium foil of thickness 20 μ m with coating process then; Toast 12h down for 90 ℃ through baking oven, under roll squeezer, pole piece compacting, branch are cut into anode pole piece then, as positive electrode.As negative electrode, positive and negative electrode capacity ratio 1: 1.15 is assembled into lithium ion battery in being full of the glove box of argon gas with the pole piece of carbon coated material on the Copper Foil.Carry out charge-discharge test with constant current, charging and discharging voltage is between 2.5～4.2V, under 25 ℃, records 0.1C and discharges and recharges down first that reversible specific capacity is 137mAh/g, and 1C first charge-discharge reversible specific capacity is 120mAh/g, and good cycling stability.
Embodiment 4
1) with LiOHH 2O, Fe (NO 3) 39H 2O, NH 4H 2PO 4And citric acid (citric acid) 1: 1: 1 in molar ratio: 1 takes by weighing raw material; Respectively it is dissolved in the deionized water; Obtain the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution respectively, wherein, the concentration of lithium hydroxide is 0.3mol/L in the aqueous solution of lithium source; The concentration of ferric nitrate is 0.3mol/L in the trivalent iron salt aqueous solution; The concentration of ammonium dihydrogen phosphate is 0.3mol/L in the aqueous phosphatic, and the concentration of citric acid is 0.3mol/L in the aqueous citric acid solution, the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume is mixed obtain mixed liquor again;
2) mixed liquor in the step 1) is poured in the autoclave, again autoclave is put into baking oven, sealing insulation 12h places cooling water with autoclave then in 160 ℃, obtains the presoma product after the cooling;
3) to step 2) in the presoma product add 6% glucose (as carbon source) with respect to presoma product total weight; Stir 8h, stir back centrifugal filtration, oven dry, again 600 ℃ of calcining 12h under nitrogen and argon shield; Wherein, The mol ratio of nitrogen and argon gas is 1: 9, and nitrogen and argon gas total gas pressure are 6MPa, obtain anode material for lithium-ion batteries LiFePO after the cooling 4/ C.
According to the X-ray diffraction map analysis, the anode material for lithium-ion batteries LiFePO that present embodiment obtains 4/ C is pure LiFePO 4Phase, carbon is non crystalline structure.Can know this anode material for lithium-ion batteries LiFePO according to stereoscan photograph 4/ C is made up of microballoon, and this diameter of micro ball is 1 μ m～3 μ m, and this microballoon is mesoporous shape.Record this anode material for lithium-ion batteries LiFePO 4Residual carbon weight percentage among the/C is 3.5%, and its actual tap density is 1.48g/cm 3
The anode material for lithium-ion batteries LiFePO that present embodiment is obtained 4/ C, conductive carbon black, polyvinylidene fluoride (PVDF, technical grade, east, Shanghai fluorine chemical Science and Technology Ltd.; Model is FR901) mixed by weight 91: 5: 4; Obtain compound, process uniform slurry for the solvent vacuum stirring with 1-methyl-2 pyrrolidones (NMP, consumption are 4.12 times of compound weight); Be coated in uniform slurry on the aluminium foil of thickness 20 μ m with coating process then; Toast 12h down for 90 ℃ through baking oven, under roll squeezer, pole piece compacting, branch are cut into anode pole piece then, as positive electrode.As negative electrode, positive and negative electrode capacity ratio 1: 1.15 is assembled into lithium ion battery in being full of the glove box of argon gas with the pole piece of carbon coated material on the Copper Foil.Carry out charge-discharge test with constant current, charging and discharging voltage is between 2.5～4.2V, under 25 ℃, records 0.1C and discharges and recharges down first that reversible specific capacity is 149mAh/g, and 1C first charge-discharge reversible specific capacity is 132mAh/g, and good cycling stability.

Claims (10)

1. anode material for lithium-ion batteries LiFePO 4The preparation method of/C may further comprise the steps:
1) lithium source, trivalent iron salt, phosphate and citric acid is soluble in water separately or together, mix and obtain mixed liquor;
2) mixed liquor in the step 1) is sealed insulation 6h～12h in 160 ℃～200 ℃, obtain the presoma product after the cooling;
3) to step 2) in the presoma product in add the glucose account for presoma product total weight 3%～10%; Stir 3h～10h; Stir back filtration, drying, 600 ℃～700 ℃ calcining 8h～12h under nitrogen and argon shield obtain anode material for lithium-ion batteries LiFePO after the cooling again 4/ C.
2. preparation method according to claim 1 is characterized in that, described lithium source is lithium acetate or lithium hydroxide, and described trivalent iron salt is Fe (NO 3) 39H 2O, described phosphate are (NH 4) H 2PO 4Or (NH 4) 2HPO 4
3. preparation method according to claim 1 is characterized in that, the mol ratio of lithium source, trivalent iron salt, phosphate, citric acid is 1～1.1 in the described mixed liquor: 1: 1: 1～1.2.
4. preparation method according to claim 1 is characterized in that the concentration of lithium source, trivalent iron salt, phosphate, citric acid is 0.3mol/L～0.5mol/L in the described mixed liquor.
5. preparation method according to claim 1 is characterized in that, the mol ratio of described nitrogen and argon gas is 3: 7～27, and the total gas pressure of described nitrogen and argon gas is 5MPa～7MPa.
6. the anode material for lithium-ion batteries LiFePO for preparing according to each described preparation method of claim 1～5 4/ C.
7. anode material for lithium-ion batteries LiFePO according to claim 6 4/ C is characterized in that, described anode material for lithium-ion batteries LiFePO 4/ C is made up of microballoon, and this diameter of micro ball is 1 μ m～3 μ m, and this microballoon is mesoporous shape.
8. anode material for lithium-ion batteries LiFePO according to claim 6 4The application of/C in preparation lithium ion battery positive electrode and lithium ion battery.
9. lithium ion battery positive electrode, process by following raw materials by weight percent:
The described anode material for lithium-ion batteries LiFePO of claim 6 4/ C 16%～20%;
Conductive carbon black 0.8%～1.2%;
Polyvinylidene fluoride 0.6%～1%;
1-Methyl-2-Pyrrolidone 78%～82%.
10. the preparation method of 9 described lithium ion battery positive electrodes as requested is characterized in that, may further comprise the steps:
With anode material for lithium-ion batteries LiFePO 4/ C, conductive carbon black and polyvinylidene fluoride mix, and add the 1-Methyl-2-Pyrrolidone vacuum stirring again and process uniform slurry, then uniform slurry are coated on the aluminium foil with coating process, and oven dry is after compacting, branch cut into positive electrode.
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WO2014056143A1 (en) * 2012-10-09 2014-04-17 上海交通大学 Lithium iron phosphate material and preparation thereof
CN103050696A (en) * 2012-12-26 2013-04-17 中国科学院深圳先进技术研究院 Nanometer lithium iron phosphate as well as preparation method and application thereof
CN103618085A (en) * 2013-12-05 2014-03-05 北京科技大学 Preparation method of metal-doped carbon coated lithium iron phosphate microspheres
CN106299355A (en) * 2015-10-15 2017-01-04 江西省金锂科技股份有限公司 A kind of preparation method of nano-carbon coated lithium iron phosphate positive material
CN106207169A (en) * 2016-08-05 2016-12-07 宁波江东仑斯福环保科技有限公司 A kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode
CN106207169B (en) * 2016-08-05 2018-12-18 周志才 A kind of preparation method of carbon gel coated LiFePO 4 for lithium ion batteries positive electrode
CN110247036A (en) * 2019-06-10 2019-09-17 张雪花 A kind of LiFePO based on lithium ion battery4Base composite positive pole and preparation method
CN112331823A (en) * 2020-10-10 2021-02-05 桂林理工大学 Lithium ion battery anode material LiFePO4Preparation method of/C
CN113651304A (en) * 2021-08-09 2021-11-16 天津理工大学 Organic carbon-coated lithium iron phosphate cathode material and preparation method thereof
CN113651304B (en) * 2021-08-09 2023-10-13 天津理工大学 Organic carbon coated lithium iron phosphate positive electrode material and preparation method thereof

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