CN102623705B - 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 PDFInfo
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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
Technical field
The present invention relates to anode material for lithium-ion batteries LiFePO
4/ C and preparation field thereof, be specifically related to a kind of hydro thermal method that adopts and prepare mesoporous microsphere shape anode material for lithium-ion batteries LiFePO
4the method of/C and the anode material for lithium-ion batteries LiFePO of preparation thereof
4/ C and application.
Background technology
Current anode material for lithium-ion batteries LiFePO
4the chemical property of/C is very significantly improved, and the specific capacity under low range almost reaches theoretical capacity, and its high-rate charge-discharge capability there has also been very large improvement.But anode material for lithium-ion batteries LiFePO
4/ C is still 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
3, but current most of anode material for lithium-ion batteries LiFePO
4the actual tap density of/C only has 1 ~ 1.4g/cm
3.
Carbon is coated can improve anode material for lithium-ion batteries LiFePO with particle size nanometer
4the high rate capability of/C, but the improvement of this performance is what to sacrifice the energy density of battery be cost.Under identical specific capacity prerequisite, the actual tap density improving material can improve the energy density of battery.Usually, anode material for lithium-ion batteries LiFePO
4the particle size of/C is less, and carbon content is more, and its actual tap density is lower, has nano-sized particles and the coated irregular anode material for lithium-ion batteries LiFePO of carbon
4the actual tap density of/C is general not higher than 1.0g/cm
3.Although mixed by machinery and can improve anode material for lithium-ion batteries LiFePO
4the actual tap density of/C, but particle shaping complex technical process.Because the spheric granules with nominal particle size is easy to be low tightly packed, therefore, the anode material for lithium-ion batteries LiFePO be made up of microsphere particle
4/ C has higher actual tap density than nano particle in irregular shape.
(H.M.Xie, R.S.Wang, R.J.Yang, the L.Zhang.Optimized LiFePO such as Xie
4-polyacene cathode material for lithium-ion batteries.Advanced Materials, 2006,18:2609-2613.) disclose with the coated LiFePO of the method synthesis carbon of crystallization control
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 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, electrolyte is difficult to penetrate 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, limit LiFePO
4the further improvement of/C microspheres with solid chemical property.
Publication number is that the Chinese patent application of CN 101299458A discloses a kind of raising anode material for lithium-ion batteries LiFePO
4the method of/C tap density, by FePO
4xH
2o and LiOHH
2o, Li
2cO
3or CH
3cOOLi2H
2o and polyethylene glycol mix, and add auxiliary agent, add the metamorphosis of water furnishing stream, and then roasting obtain anode material for lithium-ion batteries LiFePO under an inert atmosphere
4/ C.Although this technical scheme can by 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 there is good high-rate charge-discharge capability, but this anode material for lithium-ion batteries LiFePO
4the actual tap density of/C needs to improve further.
Hydro thermal method is a tiny LiFePO of synthesis
4the effective method of/C particle.Hydrothermal reaction at low temperature contributes to the control tested, but can cause LiFePO
4the degree of crystallinity of/C is very poor thus affect its chemical property.
Publication number is that the Chinese patent application of CN 101777637A discloses a kind of green LiFePO
4the preparation method of/C nano composite positive pole, a certain amount of ironic citrate, Li source compound, P source compound is taken by certain mol proportion, and be dissolved in deionized water at a certain temperature and be made into certain density mixed liquor, then certain drying mode is adopted to carry out drying, namely obtain presoma powder after grinding, presoma powder is put into sintering furnace, sinters in an inert atmosphere, then room temperature is naturally cooled to, i.e. obtained LiFePO
4/ C nano composite positive pole.Although this technical scheme obtains mixed liquor at 30 DEG C ~ 80 DEG C, and obtains presoma powder after carrying out drying, similar to hydro thermal method, as can be seen from electron microscope scanning figure, its particle diameter prepared is at about 50nm, but its nano particle out-of-shape, green LiFePO
4the actual tap density of/C nano composite positive pole 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, with the trivalent iron salt of cheapness for source of iron, adopts hydro thermal method 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, comprises the following steps:
1) lithium source, trivalent iron salt, phosphate and citric acid is soluble in water separately or together, mix and obtain mixed liquor;
2) by step 1) in mixed liquor in 160 DEG C ~ 200 DEG C close insulation 6h ~ 12h, obtain precursor product after cooling;
3) to step 2) in precursor product in add the glucose accounting for precursor product total weight 3% ~ 10%; stir 3h ~ 10h; filtration after stirring, drying; 600 DEG C ~ 700 DEG C calcining 8h ~ 12h under nitrogen and argon shield, obtain anode material for lithium-ion batteries LiFePO after cooling again
4/ C.
The present invention, by insulation 6h ~ 12h closed in 160 DEG C ~ 200 DEG C and after calcining 8h ~ 12h at 600 DEG C ~ 700 DEG C after adding glucose carbon source, obtains the anode material for lithium-ion batteries LiFePO of excellent performance
4/ C.
In order to obtain better invention effect, below as preferably of the present invention:
Described lithium source is lithium acetate or lithium hydroxide, adopts lithium acetate, lithium hydroxide as lithium source, because these two kinds of lithium sources are soluble in water and in alkalescence, and the Acidity of Aikalinity of adjustable solution and can not foreign ion be left after calcining.
Trivalent iron salt is relative to divalent iron salt, more cheap, and divalent iron salt is very easily oxidized, and further preferably, described trivalent iron salt is Fe (NO
3)
39H
2o, the nitrate ion in this trivalent iron salt and the ammonium radical ion in phosphate form ammonium nitrate and calcine rear decomposable asymmetric choice net, thus 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, and the amount taken when using on the one hand easily controls, and the ammonium radical ion in phosphate can be combined into ammonium nitrate with the nitrate ion in trivalent iron salt, contribute to decomposing.
In described mixed liquor, the mol ratio of lithium source, trivalent iron salt, phosphate, citric acid is 1 ~ 1.1: 1: 1: 1 ~ 1.2, and in described mixed liquor, the concentration of lithium source, trivalent iron salt, phosphate, citric acid is 0.3mol/L ~ 0.5mol/L.Anode material for lithium-ion batteries LiFePO is conducive to the control of material quantity and the control of material concentration
4in/C, the amount of lithium, iron and phosphoric acid remains on most suitable scope, is conducive to the anode material for lithium-ion batteries LiFePO obtaining excellent performance
4/ C.
Described nitrogen and the mol ratio of argon gas are 3: 7 ~ 27, and described nitrogen and the total gas pressure of argon gas are 5MPa ~ 7MPa.The present invention adopts nitrogen and argon gas two kinds of gases, on the one hand the price of nitrogen is relative to lower argon gas, lower than the simple argon gas cost that uses, on the other hand, ratio and the total gas pressure of nitrogen and argon gas are limited to preferable range, provide a stable calcination environment, in calcination process, remove the unstable impurity that generates in preparation process as while ammonium nitrate, avoid the introducing of other impurity.
Present invention also offers anode material for lithium-ion batteries LiFePO prepared by a kind of described preparation method
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 the diameter of this microballoon is 1 μm ~ 3 μm, 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
4/ C is preparing the application in lithium ion battery positive electrode and lithium ion battery.
A kind of lithium ion battery positive electrode, be made up of the raw material of following percentage by weight:
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, comprises the following steps:
By anode material for lithium-ion batteries LiFePO
4/ C, conductive carbon black and polyvinylidene fluoride mix, then add 1-Methyl-2-Pyrrolidone vacuum stirring and make uniform slurry, are then coated on aluminium foil by uniform slurry coating process, after oven dry through compacting, point cut into positive electrode.Be used in lithium ion battery by the positive electrode of preparation, this lithium ion battery has higher specific capacity.
Compared with prior art, tool of the present invention has the following advantages:
Anode material for lithium-ion batteries LiFePO of the present invention
4in the preparation method of/C, using the trivalent iron salt of cheapness as source of iron, hydro thermal method simple and easy to control is adopted to prepare anode material for lithium-ion batteries LiFePO
4/ C, in the incipient stage of hydro-thermal reaction, the granular precursor of nano-scale is had to deposit because presoma solubility in mixed liquor reduces, a nano particle (i.e. nano particle of these dispersions, particle diameter is about 100nm) surface instability, for reducing interfacial tension, they are agglomerated into fine and close microballoon (secondary microballoon), along with the prolongation of time under 160 DEG C ~ 200 DEG C high temperature, pressure increases, these secondary microballoons of reuniting can experience the process of one section of dissolution-deposition, in this course, the microballoon of the densification be agglomerated into is etched into meso-hole structure, these mesoporous shape microballoon presomas form single-phase anode material for lithium-ion batteries LiFePO after 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.
Anode material for lithium-ion batteries LiFePO prepared by the present invention
4/ C is made up of microballoon, and the diameter of this microballoon is 1 μm ~ 3 μm, and have high-tap density, this microballoon is mesoporous shape, and the meso-hole structure on microballoon contributes to electrolyte permeability and enters microballoon inside, and electrolyte is fully contacted with active material.Meanwhile, the conducting path of the specific area that nano particle is larger and shorter electronics and ion, thus its chemical property can be improved.Therefore, the anode material for lithium-ion batteries LiFePO for preparing of the present invention
4/ C possesses high-tap density simultaneously, and lithium ion battery prepared by this material 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
4lithium ion battery prepared by/C 20C multiplying power discharging specific capacity at room temperature 25 DEG C is 102mAh/g, the requirement of power-type lithium ion battery can be met, and preparation method of the present invention has, and needed raw material cost is lower, preparation method is simple, process is easy to control, low power consumption and other advantages, is suitable for large-scale production.
Accompanying drawing explanation
Fig. 1 is anode material for lithium-ion batteries LiFePO prepared by embodiment 1
4the X-ray diffractogram of/C;
Fig. 2 is anode material for lithium-ion batteries LiFePO prepared by embodiment 1
4(100K doubly) stereoscan photograph of/C;
Fig. 3 is anode material for lithium-ion batteries LiFePO prepared by embodiment 1
4(20K doubly) stereoscan photograph of/C;
Fig. 4 is the specific capacity curve testing continuous 10 charge and discharges circulation after the lithium ion battery of embodiment 1 preparation recycles under different multiplying.
Embodiment
Be described in detail the present invention below in conjunction with embodiment, following examples do not produce restriction to the present invention.
Embodiment 1
1) by LiOHH
2o, Fe (NO
3)
39H
2o, NH
4h
2pO
4raw material is taken at 1: 1: 1: 1 in molar ratio with citric acid (citric acid), be dissolved in respectively in deionized water, obtain the lithium source aqueous solution respectively, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution, wherein, in the aqueous solution of lithium source, the concentration of lithium hydroxide is 0.3mol/L, in the trivalent iron salt aqueous solution, the concentration of ferric nitrate is 0.3mol/L, in aqueous phosphatic, the concentration of ammonium dihydrogen phosphate is 0.3mol/L, in aqueous citric acid solution, the concentration of citric acid is 0.3mol/L, again by the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume mixes and obtains mixed liquor,
2) by step 1) in mixed liquor pour in autoclave, then autoclave is put into baking oven, in 180 DEG C, closes insulation 10h, then autoclave is placed in cooling water, after cooling, obtains precursor product;
3) to step 2) in precursor product add relative to precursor product total weight 5% glucose (as carbon source); stir 5h; centrifugal filtration after stirring, oven dry; 650 DEG C of calcining 10h under nitrogen and argon shield again; 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 cooling
4/ C.
The anode material for lithium-ion batteries LiFePO that the present embodiment obtains
4the X-ray diffractogram of/C as shown in Figure 1, is pure LiFePO
4phase, carbon is non crystalline structure.The anode material for lithium-ion batteries LiFePO that the present embodiment obtains
4the stereoscan photograph of/C as shown in Figure 2,3; As shown in Figure 2,3, this anode material for lithium-ion batteries LiFePO
4/ C is made up of microballoon, and the diameter of this microballoon is 1 μm ~ 3 μm, 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 in/C is 2.65%, and its actual tap density is 1.51g/cm
3.
The anode material for lithium-ion batteries LiFePO that the 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) by weight 91: 5: 4 mixing, obtain compound, with 1-Methyl-2-Pyrrolidone (NMP, consumption is 4.12 times of compound weight) make uniform slurry for solvent in vacuo stirs, then uniform slurry coating process is coated on the aluminium foil of thickness 20 μm, 12h is toasted at 90 DEG C, baking oven, then under roll squeezer by pole piece compacting, point cut into anode pole piece, as positive electrode.On Copper Foil, the pole piece of carbon coating material is as negative electrode, positive and negative electrode capacity ratio 1: 1.15, in the glove box being full of argon gas, be assembled into lithium ion battery.Charge-discharge test is carried out with constant current, charge and discharge voltage is between 2.5 ~ 4.2V, the specific capacity of its battery first charge-discharge under (0.1C, 1C, 5C, 10C, 20C) different multiplying at 25 DEG C is as shown in table 1, recording under 0.1C discharge and recharge reversible specific capacity is first 155mAh/g, 1C first charge-discharge reversible specific capacity is 137mAh/g, 5C first charge-discharge reversible specific capacity is 118mAh/g, 10C first charge-discharge reversible specific capacity is 109mAh/g, 20C first charge-discharge reversible specific capacity is 102mAh/g.The specific capacity curve of continuous 10 charge and discharges circulation is tested as shown in Figure 4 after this lithium ion battery recycling under different multiplying, each through 10 charge and discharge stable cycle performance under many multiplying powers.
Table 1
Embodiment 2
1) by CH
3cOOLi2H
2o, Fe (NO
3)
39H
2o, NH
4h
2pO
4raw material is taken at 1.05: 1: 1: 1 in molar ratio with citric acid (citric acid), be dissolved in respectively in deionized water, obtain the lithium source aqueous solution respectively, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution, wherein, in the aqueous solution of lithium source, the concentration of lithium acetate is 0.4mol/L, in the trivalent iron salt aqueous solution, the concentration of ferric nitrate is 0.4mol/L, in aqueous phosphatic, the concentration of ammonium dihydrogen phosphate is 0.4mol/L, in aqueous citric acid solution, the concentration of citric acid is 0.4mol/L, again by the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume mixes and obtains mixed liquor,
2) by step 1) in mixed liquor pour in autoclave, then autoclave is put into baking oven, in 180 DEG C, closes insulation 10h, then autoclave is placed in cooling water, after cooling, obtains precursor product;
3) to step 2) in precursor product add relative to precursor product total weight 5% glucose (as carbon source); stir 5h; centrifugal filtration after stirring, oven dry; 650 DEG C of calcining 10h under nitrogen and argon shield again; 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 cooling
4/ C.
According to X-ray diffraction map analysis, the anode material for lithium-ion batteries LiFePO that the present embodiment obtains
4/ C is pure LiFePO
4phase, carbon is non crystalline structure.According to stereoscan photograph, this anode material for lithium-ion batteries LiFePO
4/ C is made up of microballoon, and the diameter of this microballoon is 1 μm ~ 3 μm, and this microballoon is mesoporous shape.Record this anode material for lithium-ion batteries LiFePO
4residual carbon weight percentage in/C is 6.3%, and its actual tap density is 1.47g/cm
3.
The anode material for lithium-ion batteries LiFePO that the 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) by weight 91: 5: 4 mixing, obtain compound, with 1-methyl-2 pyrrolidones (NMP, consumption is 4.12 times of compound weight) make uniform slurry for solvent in vacuo stirs, then uniform slurry coating process is coated on the aluminium foil of thickness 20 μm, 12h is toasted at 90 DEG C, baking oven, then under roll squeezer by pole piece compacting, point cut into anode pole piece, as positive electrode.On Copper Foil, the pole piece of carbon coating material is as negative electrode, positive and negative electrode capacity ratio 1: 1.15, in the glove box being full of argon gas, be assembled into lithium ion battery.Carry out charge-discharge test with constant current, charge and discharge voltage is between 2.5 ~ 4.2V, and at 25 DEG C, to record under 0.1C discharge and recharge that reversible specific capacity is 145mAh/g, 1C first charge-discharge reversible specific capacity is first 127mAh/g, and good cycling stability.
Embodiment 3
1) by LiOHH
2o, Fe (NO
3)
39H
2o, NH
4h
2pO
4raw material is taken at 1: 1: 1: 1 in molar ratio with citric acid (citric acid), be dissolved in respectively in deionized water, obtain the lithium source aqueous solution respectively, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution, wherein, in the aqueous solution of lithium source, the concentration of lithium hydroxide is 0.5mol/L, in the trivalent iron salt aqueous solution, the concentration of ferric nitrate is 0.5mol/L, in aqueous phosphatic, the concentration of ammonium dihydrogen phosphate is 0.5mol/L, in aqueous citric acid solution, the concentration of citric acid is 0.5mol/L, again by the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume mixes and obtains mixed liquor, 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) by step 1) in mixed liquor pour in autoclave, then autoclave is put into baking oven, in 200 DEG C, closes insulation 12h, then autoclave is placed in cooling water, after cooling, obtains precursor product;
3) to step 2) in precursor product add relative to precursor product total weight 5% glucose (as carbon source); stir 5h; centrifugal filtration after stirring, oven dry; 700 DEG C of calcining 12h under nitrogen and argon shield again; 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 cooling
4/ C.
According to X-ray diffraction map analysis, the anode material for lithium-ion batteries LiFePO that the present embodiment obtains
4/ C is pure LiFePO
4phase, carbon is non crystalline structure.According to stereoscan photograph, this anode material for lithium-ion batteries LiFePO
4/ C is made up of microballoon, and the diameter of this microballoon is 1 μm ~ 3 μm, and this microballoon is mesoporous shape.Record this anode material for lithium-ion batteries LiFePO
4residual carbon weight percentage in/C is 1.7%, and its actual tap density is 1.54g/cm
3.
The anode material for lithium-ion batteries LiFePO that the 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) by weight 91: 5: 4 mixing, obtain compound, with 1-methyl-2 pyrrolidones (NMP, consumption is 4.12 times of compound weight) make uniform slurry for solvent in vacuo stirs, then uniform slurry coating process is coated on the aluminium foil of thickness 20 μm, 12h is toasted at 90 DEG C, baking oven, then under roll squeezer by pole piece compacting, point cut into anode pole piece, as positive electrode.On Copper Foil, the pole piece of carbon coating material is as negative electrode, positive and negative electrode capacity ratio 1: 1.15, in the glove box being full of argon gas, be assembled into lithium ion battery.Carry out charge-discharge test with constant current, charge and discharge voltage is between 2.5 ~ 4.2V, and at 25 DEG C, to record under 0.1C discharge and recharge that reversible specific capacity is 137mAh/g, 1C first charge-discharge reversible specific capacity is first 120mAh/g, and good cycling stability.
Embodiment 4
1) by LiOHH
2o, Fe (NO
3)
39H
2o, NH
4h
2pO
4raw material is taken at 1: 1: 1: 1 in molar ratio with citric acid (citric acid), be dissolved in respectively in deionized water, obtain the lithium source aqueous solution respectively, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution, wherein, in the aqueous solution of lithium source, the concentration of lithium hydroxide is 0.3mol/L, in the trivalent iron salt aqueous solution, the concentration of ferric nitrate is 0.3mol/L, in aqueous phosphatic, the concentration of ammonium dihydrogen phosphate is 0.3mol/L, in aqueous citric acid solution, the concentration of citric acid is 0.3mol/L, again by the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume mixes and obtains mixed liquor,
2) by step 1) in mixed liquor pour in autoclave, then autoclave is put into baking oven, in 160 DEG C, closes insulation 12h, then autoclave is placed in cooling water, after cooling, obtains precursor product;
3) to step 2) in precursor product add relative to precursor product total weight 6% glucose (as carbon source); stir 8h; centrifugal filtration after stirring, oven dry; 600 DEG C of calcining 12h under nitrogen and argon shield again; 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 cooling
4/ C.
According to X-ray diffraction map analysis, the anode material for lithium-ion batteries LiFePO that the present embodiment obtains
4/ C is pure LiFePO
4phase, carbon is non crystalline structure.According to stereoscan photograph, this anode material for lithium-ion batteries LiFePO
4/ C is made up of microballoon, and the diameter of this microballoon is 1 μm ~ 3 μm, and this microballoon is mesoporous shape.Record this anode material for lithium-ion batteries LiFePO
4residual carbon weight percentage in/C is 3.5%, and its actual tap density is 1.48g/cm
3.
The anode material for lithium-ion batteries LiFePO that the 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) by weight 91: 5: 4 mixing, obtain compound, with 1-methyl-2 pyrrolidones (NMP, consumption is 4.12 times of compound weight) make uniform slurry for solvent in vacuo stirs, then uniform slurry coating process is coated on the aluminium foil of thickness 20 μm, 12h is toasted at 90 DEG C, baking oven, then under roll squeezer by pole piece compacting, point cut into anode pole piece, as positive electrode.On Copper Foil, the pole piece of carbon coating material is as negative electrode, positive and negative electrode capacity ratio 1: 1.15, in the glove box being full of argon gas, be assembled into lithium ion battery.Carry out charge-discharge test with constant current, charge and discharge voltage is between 2.5 ~ 4.2V, and at 25 DEG C, to record under 0.1C discharge and recharge that reversible specific capacity is 149mAh/g, 1C first charge-discharge reversible specific capacity is first 132mAh/g, and good cycling stability.
Claims (1)
1. an anode material for lithium-ion batteries LiFePO
4the preparation method of/C, is characterized in that, comprises the following steps:
1) by LiOHH
2o, Fe (NO
3)
39H
2o, NH
4h
2pO
4with citric acid in molar ratio 1:1:1:1 take raw material, be dissolved in respectively in deionized water, obtain the lithium source aqueous solution respectively, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution, wherein, in the aqueous solution of lithium source, the concentration of lithium hydroxide is 0.3mol/L, in the trivalent iron salt aqueous solution, the concentration of ferric nitrate is 0.3mol/L, in aqueous phosphatic, the concentration of ammonium dihydrogen phosphate is 0.3mol/L, in aqueous citric acid solution, the concentration of citric acid is 0.3mol/L, again by the lithium source aqueous solution, the trivalent iron salt aqueous solution, aqueous phosphatic, aqueous citric acid solution equal-volume mixes and obtains mixed liquor,
2) mixed liquor in step 1) is poured in autoclave, then autoclave is put into baking oven, in 180 DEG C, close insulation 10h, then autoclave is placed in cooling water, after cooling, obtains precursor product;
3) to step 2) in precursor product add relative to precursor product total weight 5% glucose; stir 5h; centrifugal filtration after stirring, oven dry; 650 DEG C of calcining 10h under nitrogen and argon shield again; 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 cooling
4/ C.
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| CN201210092411.9A CN102623705B (en) | 2012-03-30 | 2012-03-30 | Lithium ion battery cathode material LiFePO4/C, and preparation method and application thereof |
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| CN103050696B (en) * | 2012-12-26 | 2014-09-17 | 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 |
| CN103618085B (en) * | 2013-12-05 | 2015-10-21 | 北京科技大学 | A kind of preparation method of metal-doped carbon-coated LiFePO 4 for lithium ion batteries microballoon |
| 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 |
| 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 |
| CN110247036B (en) * | 2019-06-10 | 2022-11-18 | 湖南顺华锂业有限公司 | LiFePO based on lithium ion battery 4 Base composite anode material and preparation method thereof |
| CN112331823A (en) * | 2020-10-10 | 2021-02-05 | 桂林理工大学 | Lithium ion battery anode material LiFePO4Preparation method of/C |
| 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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| Template-Free Hydrothermal Synthesis of Nanoembossed Mesoporous LiFePO4 Microspheres for High-Performance Lithium-Ion Batteries;Jiangfeng Qian等;《The Journal of Physical Chemistry C》;20100209;第114卷;第3477-3482页 * |
| 陈召勇,朱华丽.LiFePO4/C复合材料的制备和性能研究.《长沙理工大学学报(自然科学版)》.2007,第4卷(第2期), * |
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