CN103618065A - Lithium iron phosphate material and preparation method thereof - Google Patents
Lithium iron phosphate material and preparation method thereof Download PDFInfo
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- CN103618065A CN103618065A CN201310586823.2A CN201310586823A CN103618065A CN 103618065 A CN103618065 A CN 103618065A CN 201310586823 A CN201310586823 A CN 201310586823A CN 103618065 A CN103618065 A CN 103618065A
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides a lithium iron phosphate material, which contains a main carbon source and tungsten carbide in a carbon coating material. Furthermore, the invention provides a preparation method of the lithium iron phosphate material. The preparation method comprises the following steps: mixing a lithium source, a phosphorus source, an iron source, a main carbon source and tungsten carbide, ball-milling, drying, grinding and baking to obtain the lithium iron phosphate material. The lithium iron phosphate material disclosed by the invention not only optimizes electrochemical performance of carbon coating and reduces carbon content, but also improves reaction efficiency. The adopted raw materials are wide in source, easily available and cheap, and the prepared lithium iron phosphate material is free from heavy metal elements which cause serious pollution to the environment and is environment-friendly. The lithium iron phosphate material is stable in charge/discharge voltage platform, and is excellent in electrical conductivity and high current charge/discharge performance. And through the tungsten carbide which is a good electrical and thermal conductor, the lithium iron phosphate material has the characteristics of stable structure, good thermal stability and excellent circulating performance.
Description
Technical field
The present invention relates to a kind of preparation method of anode composite material of lithium ion battery, particularly a kind of tungsten carbide and carbon are coated the preparation method of LiFePO4 (LiFePO4) positive electrode of activation altogether.
Background technology
Under energy crisis and environmental protection dual-pressure, countries in the world are formulated the target of energy-saving and emission-reduction one after another, adopt an effective measure and realize economic Green Development, the transition of finally realizing economic structure, realize the transformation of low-carbon economy.LiFePO 4 material because have security performance good, have extended cycle life, aboundresources, advantages of environment protection, by international power supply, being known as is lithium ion power and the energy-storage battery positive electrode of tool future, development to ev industry and novel energy-storing industry has great significance, market prospects are wide, and social influence is huge.LiFePO 4 material and battery thereof have become the strategic industry direction of the focus and emphasis investment that each Main Developed Countries of the world competitively researchs and develops.But LiFePO4 has conductivity low, poor performance at low temperatures, tap density is lower, and preparation technology's high in cost of production shortcoming, for these problems, also needs further Improvement.
Low and the slow shortcoming of lithium ion diffusion rate for the electronic conductivity of LiFePO4, researchers have carried out a lot of effort, the method of taking comprises that element mixes up, surface is coated or modifies, by reducing particle size, changes its charge-discharge mechanism and find solid solution etc., the LiFePO4 of the growth of controlledly synthesis crystal plane orientation in addition, is also an important research direction.
Carbon is coated is study often and realized industrialized method in LiFePO4 surface is coated, and the good conductivity of material with carbon element and cheap, when improving conductivity, can also improve nucleation rate, suppresses particle and grows up.Carbon is coated generally two kinds of approach: the one, and high-temperature roasting after carbon dust is mixed with raw material in certain proportion; The 2nd, in the precursor of LiFePO4, add carbonaceous organic material, carry out afterwards pyroreaction, when forming LiFePO4, on its surface, form carbon coating layer.The chemical property of carbon-coated LiFePO 4 for lithium ion batteries and carbon source used, the carbon content of composite material and the decentralization of carbon have much relations.Although LiFePO4 is carried out to carbon to be coated on and to have improved to a great extent its conductivity, but the introducing of this inert matter, caused the reduction of whole electrode specific capacity, especially the low-density of material with carbon element, reduce the tap density of electrode material, reduced volume and capacity ratio and the energy density of electrode.In addition, utilize material with carbon element to carry out the method for coated LiFePO 4 for lithium ion batteries particle, be mainly the conductivity having changed between particle and particle, and the conductivity of lithium iron phosphate particles inside affected very micro-.Therefore, coated ionic conductance and the chemical diffusion coefficient of lithium ion in LiFePO4 that do not improve in itself of carbon.
With metallic particles or conductive compound, also can improve electron conductivity and the ionic conductance of material, stop the growth of lithium iron phosphate particles, make the particle that particle diameter is less, make Li
+diffusion length reduce, increase FePO
4and LiFePO
4contact area, thereby make lithium ion Li
+can be at larger FePO
4/ LiFePO
4on interface, spread.The people such as Croce (DOI:10.1149/1.1449302) adopt respectively 1% Cu and the coated method of Ag powder, the sample initial discharge specific capacity of preparation has improved 25mAh/g, and infer that coated metal powder can play conducting bridge between LiFePO4 particle, thereby improve LiFePO
4discharge performance.Y. people (the DOI such as Lin
:10.1016/j.matchemphys.2012.11.062) utilize hydro thermal method to synthesize to there is better cycle performance and compared with the LiFePO of high-discharge-rate
4/ Si composite material, and under high temperature, performance is more outstanding.This is mainly the introducing due to Si, when having reduced electric charge transmission resistance, has also improved lithium ion Li
+diffusion coefficient.This free bond energy that can be interpreted as Si and fluorosilicone compound is enough suppressed Fe
2+from the decomposition of olivine phase, and stop sheet resistance and electric charge to transmit the increase of resistance.
Yet, coated similar to carbon, these coated LiFePO that also fundamentally do not improve
4conductivity.
Summary of the invention
Object of the present invention is exactly in order to overcome the deficiencies in the prior art, and a kind of LiFePO 4 material is provided, thereby optimizes the chemical property of lithium iron phosphate positive material.For this reason, the present invention by the following technical solutions: in its carbon encapsulated material, except main body carbon source, also contain tungsten carbide.
Another technical problem to be solved of the present invention is to provide a kind of preparation method of above-mentioned LiFePO 4 material, for this reason, the present invention by the following technical solutions: described preparation method comprises the following steps: it comprises the following steps: ,Lin source, lithium source, source of iron, main body carbon source and tungsten carbide mixing, ball milling, dry, pulverizing, roasting are made to above-mentioned LiFePO 4 material.
Adopting on the basis of technique scheme, the present invention also can adopt following further technical scheme:
Mix in proportion in described lithium source, source of iron and phosphorus source, and wherein Li:Fe:P mol ratio is (0.95-1.05): 1:1.
Described lithium source comprises one or more in lithium dihydrogen phosphate, lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate.
Described source of iron comprises one or more of ferric phosphate, ferrous oxalate, ferrous acetate, di-iron trioxide, ferric nitrate, ironic citrate etc.
Described phosphorus source comprises one or more in ferric phosphate, phosphorus pentoxide, phosphoric acid, ammonium phosphate, pyrophosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
Described dominant carbon source material comprises one or more in glucose, sucrose, polypropylene, polyacrylamide, polyvinyl alcohol, soluble starch, Graphene, citric acid, carbon nano-tube, acetylene black, carbon black.
The dominant carbon source quality adding is the 25%-60% of lithium source quality; After sintering, the phosphorus content mass percent of LiFePO 4 powder material is between 1.2%-1.8%.
The quality that adds tungsten carbide is that 0.005-0.5g/mol(is in every mole of phosphoric acid iron lithium).
Described ball grinding method is wet method, and blending agent is deionized water, absolute ethyl alcohol, acetone or industrial alcohol, and the ratio of blending agent is the 75%-150% of solid phase gross mass, just to have mobility, is advisable; The incorporation time of liquid phase batch mixing is preferably 4-12 hour; To be mixed evenly and after dry, put into carbon and bury the reducing atmosphere covering and carry out sintering; Be warming up to 350-450 ℃ and carry out pre-burning, heating rate is preferably 1-5 ℃/min, constant temperature time 1-3 hour; Be warming up to 650-750 ℃ and calcine, heating rate is preferably 1-5 ℃/min, constant temperature time 6-12 hour.
Compared with prior art, tool has the following advantages in the present invention:
Tungsten carbide (WC) Electronic Structure and platinum (Pt) are similar, have certain catalytic activity in chemical reaction, and are electricity and hot good conductor; Compare with platinum (Pt), tungsten carbide (WC) belongs to nonmetal, when improving conductivity of lithium iron phosphate material, can not affect the crystalline form of LiFePO 4 material, and the dispersive property in material with carbon element is better, improves the conduction uniformity of LiFePO 4 material.Material with carbon element has larger specific area, abundant pore structure and unique surface chemical property, useful as catalysts carrier and battery electrode component etc., and it is during as catalyst carrier, well dispersed activity component and auxiliary agent.The double catalyst of doing conductive agent and solid phase reaction and electrochemical reaction of tungsten carbide of the present invention, and play the effect that promotes particle mixing, refinement particle, dominant carbon source material is as catalyst carrier and conductive agent.
The present invention adds by tungsten carbide, has not only optimized the coated chemical property of carbon, has also reduced carbon content.Meanwhile, tungsten carbide is as the catalyst of solid phase reaction, and material with carbon element, as catalyst carrier, can improve reaction efficiency.The raw material wide material sources that adopt, be easy to get, cheap, the LiFePO 4 material of preparation is containing environment being had to the heavy metal element of larger pollution, environmental friendliness.This LiFePO 4 material has stable charging/discharging voltage platform, and electric conductivity and high rate during charging-discharging are good.And tungsten carbide, as electricity and hot good conductor, makes this lithium iron phosphate positive material have the features such as Stability Analysis of Structures, thermal stability is good, cycle performance is good.
Carbon in the present invention buries and covers reducing atmosphere sintering process roasting technique is simplified, and with low costization, when reducing production costs, in the time of Optimization Technology, further enhances productivity and consistency, is convenient to carry out large-scale production.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum (XRD) of the coated lithium iron phosphate positive material (b) of the coated lithium iron phosphate positive material (a) of the common carbon of the prepared tungsten carbide of the embodiment of the present invention 1 and pure carbon.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) that the prepared tungsten carbide of the embodiment of the present invention 1 is total to the coated lithium iron phosphate positive material of carbon.
Fig. 3 is that common coated lithium iron phosphate positive material (a) and the coated lithium iron phosphate positive material (b) of pure carbon of carbon of the prepared tungsten carbide of the embodiment of the present invention 1 is assembled into 0.2C charging and discharging curve and the 2C charging and discharging curve after button cell, charging/discharging voltage scope is 2.0-4.0V, the LiPF that electrolyte is 1mol/L
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1).
Fig. 4 is that the common coated lithium iron phosphate positive material of carbon of the prepared tungsten carbide of the embodiment of the present invention 1 is assembled into the cycle performance schematic diagram after button cell.Charge-discharge magnification is 2C, and charging/discharging voltage scope is 2.0-4.0V, the LiPF that electrolyte is 1mol/L
6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1).
Embodiment
The present embodiment be take technical solution of the present invention and is implemented as prerequisite, but protection scope of the present invention is not limited only to following example.
Embodiment 1:
Lithium hydroxide, ferrous oxalate, ammonium dihydrogen phosphate are pressed to ion mol ratio Li
+: Fe
2+: PO
4 3-=1.005:1.00:1.00 weighs, and by 26% of lithium hydroxide quality, adds glucose, by the amount of 0.01g/mol, adds tungsten carbide, by 80% of reaction mass gross mass, add absolute ethyl alcohol again, ball milling mixed after 6 hours, and the slurry that obtains mixing, after 80 ℃ of forced air dryings, being placed on carbon buries in the closed container covering, put into Muffle furnace, with the heating rate of 5 ℃/min, be warming up to 400 ℃, be incubated 1 hour, with 2 ℃/min, be warming up to 700 ℃ again, be incubated 10 hours.With stove, naturally cool to room temperature, obtain the common coated lithium iron phosphate positive material LiFePO of tungsten carbide and carbon
4/ C/WC.
In order relatively to need, also under identical preparation condition and composition and ratio, prepared respectively the coated lithium iron phosphate positive material of pure carbon.
Tungsten carbide prepared by said method altogether coated lithium iron phosphate positive material and the coated lithium iron phosphate positive material of pure carbon of carbon carries out powder X-ray diffraction, and its collection of illustrative plates as shown in Figure 1.As seen from Figure 1, the diffraction maximum of the lithium iron phosphate positive material (b) that the lithium iron phosphate positive material (a) that the common carbon of tungsten carbide is coated and pure carbon are coated is basic identical, the crystal structure that does not change LiFePO4 that adds of minute quantity tungsten carbide is described, and does not have impurity phase to generate.ESEM (SEM) collection of illustrative plates of the lithium iron phosphate positive material that the common carbon of tungsten carbide is coated as shown in Figure 2, material consists of lamina block not of uniform size, granular size 0.5-2 μ m, less particle and laminar structured favourable to improving lithium ion and the electron mobility of LiFePO4 bulk material, thus ionic conduction efficiency improved.
The composite material making is made to electrode as follows:
82:10:8 takes respectively composite material, acetylene black and polytetrafluoroethylene in mass ratio, makes cathode film; Pure metal lithium sheet is as negative pole; Barrier film is import microporous polypropylene membrane (Celgard 2400); Electrolyte is 1mol/L LiPF6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1:1), in the glove box of applying argon gas, is assembled into button cell.In order relatively to need, the lithium iron phosphate positive material coated to the pure carbon of preparing under the same terms is also assembled into button cell according to above-mentioned technique.Above battery is carried out to 0.2C and 2C charge-discharge test under room temperature, and charging/discharging voltage scope is 2.0-4.0V.As shown in Figure 3, tungsten carbide altogether coated lithium iron phosphate positive material (a) lithium iron phosphate positive material (b) coated with pure carbon of carbon is compared, and has higher specific capacity under 0.2C, is respectively 157 mAh/g and 152 mAh/g; And under high magnification, the tungsten carbide altogether coated lithium iron phosphate positive material of carbon has higher capability retention (under 2C multiplying power, being respectively 145 mAh/g and 134 mAh/g) and more excellent platform voltage.Fig. 4 is the altogether cycle performance schematic diagram under the 2C multiplying power of the coated lithium iron phosphate positive material (a) of carbon and the coated lithium iron phosphate positive material (b) of pure carbon of tungsten carbide, as seen from Figure 4, the tungsten carbide altogether coated lithium iron phosphate positive material of carbon has more stable cycle performance, under high magnification, be stabilising decay trend, and attenuation rate is low.Visible, the tungsten carbide altogether coated lithium iron phosphate positive material of carbon has potential using value in power and energy-storage battery application.
Embodiment 2:
Lithium carbonate, ferric phosphate are pressed to ion mol ratio Li
+: Fe
3+: PO
4 3-=1.01:1.00:1.00 weighs, and by 35% of lithium hydroxide quality, adds sucrose, by the amount of 0.005g/mol, adds tungsten carbide, by 75% of reaction mass gross mass, add absolute ethyl alcohol again, ball milling mixed after 4 hours, and the slurry that obtains mixing, after 85 ℃ of forced air dryings, being placed on carbon buries in the closed container covering, put into Muffle furnace, with the heating rate of 2 ℃/min, be warming up to 400 ℃, be incubated 2 hours, with 5 ℃/min, be warming up to 720 ℃ again, be incubated 10 hours.With stove, naturally cool to room temperature, obtain the common coated lithium iron phosphate positive material LiFePO of tungsten carbide and carbon
4/ C/WC.By the method for embodiment 1, prepare cathode film equally, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recording is respectively 155mAh/g and 143mAh/g.
Embodiment 3:
Lithium hydroxide, ferrous acetate, ammonium dihydrogen phosphate are pressed to ion mol ratio Li
+: Fe
2+: PO
4 3-=1.02:1.00:1.00 weighs, and by 40% of lithium hydroxide quality, adds citric acid, by the amount of 0.02g/mol, adds tungsten carbide, by 90% of reaction mass gross mass, add absolute ethyl alcohol again, after ball milling mixes hour, the slurry that obtains mixing, after 90 ℃ of forced air dryings, being placed on carbon buries in the closed container covering, put into Muffle furnace, with the heating rate of 5 ℃/min, be warming up to 400 ℃, be incubated 3 hours, with 2 ℃/min, be warming up to 750 ℃ again, be incubated 8 hours.With stove, naturally cool to room temperature, obtain the common coated lithium iron phosphate positive material LiFePO of tungsten carbide and carbon
4/ C/WC.By the method for embodiment 1, prepare cathode film equally, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recording is respectively 158mAh/g and 147mAh/g.
Embodiment 4:
Ferrous oxalate, lithium dihydrogen phosphate are pressed to ion mol ratio Li
+: Fe
2+: PO
4 3-=1.00:1.00:1.00 weighs, and by 40% of the lithium hydroxide quality of amount of substance such as grade, adds polyvinyl alcohol, by the amount of 0.05g/mol, adds tungsten carbide, by 100% of reaction mass gross mass, add absolute ethyl alcohol again, ball milling mixed after 10 hours, and the slurry that obtains mixing, after 100 ℃ of forced air dryings, being placed on carbon buries in the closed container covering, put into Muffle furnace, with the heating rate of 5 ℃/min, be warming up to 400 ℃, be incubated 3 hours, with 5 ℃/min, be warming up to 680 ℃ again, be incubated 10 hours.With stove, naturally cool to room temperature, obtain the common coated lithium iron phosphate positive material LiFePO of tungsten carbide and carbon
4/ C/WC.By the method for embodiment 1, prepare cathode film equally, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recording is respectively 151mAh/g and 140mAh/g.
Embodiment 5:
Lithium hydroxide, ferrous oxalate, ammonium dihydrogen phosphate are pressed to ion mol ratio Li
+: Fe
2+: PO
4 3-=1.05:1.00:1.00 weighs, and by 30% of lithium hydroxide quality, adds glucose, by the amount of 0.04g/mol, adds tungsten carbide, by 150% of reaction mass gross mass, add absolute ethyl alcohol again, ball milling mixed after 5 hours, and the slurry that obtains mixing, after 80 ℃ of forced air dryings, being placed on carbon buries in the closed container covering, put into Muffle furnace, with the heating rate of 5 ℃/min, be warming up to 350 ℃, be incubated 3 hours, with 2 ℃/min, be warming up to 750 ℃ again, be incubated 6 hours.With stove, naturally cool to room temperature, obtain the common coated lithium iron phosphate positive material LiFePO of tungsten carbide and carbon
4/ C/WC.By the method for embodiment 1, prepare cathode film equally, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recording is respectively 159mAh/g and 144mAh/g.
Embodiment 6:
Lithium acetate, di-iron trioxide, ammonium dihydrogen phosphate are pressed to ion mol ratio Li
+: Fe
3+: PO
4 3-=1.04:1.00:1.00 weighs, and by 60% of the lithium hydroxide quality of amount of substance such as grade, adds soluble starch, by the amount of 0.015g/mol, adds tungsten carbide, by 120% of reaction mass gross mass, add absolute ethyl alcohol again, ball milling mixed after 6 hours, and the slurry that obtains mixing, after 95 ℃ of forced air dryings, being placed on carbon buries in the closed container covering, put into Muffle furnace, with the heating rate of 5 ℃/min, be warming up to 450 ℃, be incubated 2 hours, with 3 ℃/min, be warming up to 650 ℃ again, be incubated 10 hours.With stove, naturally cool to room temperature, obtain the common coated lithium iron phosphate positive material LiFePO of tungsten carbide and carbon
4/ C/WC.By the method for embodiment 1, prepare cathode film equally, be assembled into after battery respectively with 0.2C and 2C rate charge-discharge, the reversible capacity recording is respectively 153mAh/g and 141mAh/g.
Above-described embodiment is preferably embodiment of the present invention; but embodiment of the present invention are not restricted to the described embodiments; other are any do not deviate from Spirit Essence of the present invention and principle change, modification, substitute, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. LiFePO 4 material, is characterized in that in its carbon encapsulated material, except main body carbon source, also containing tungsten carbide.
2. the preparation method of LiFePO 4 material as claimed in claim 1, is characterized in that it comprises the following steps: ,Lin source, lithium source, source of iron, main body carbon source and tungsten carbide mixing, ball milling, dry, pulverizing, roasting are made to LiFePO 4 material claimed in claim 1.
3. preparation method as claimed in claim 2, is characterized in that described lithium source, source of iron and phosphorus source mix in proportion, and wherein Li:Fe:P mol ratio is (0.95-1.05): 1:1.
4. preparation method as claimed in claim 2, is characterized in that described lithium source comprises one or more in lithium dihydrogen phosphate, lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate.
5. preparation method as claimed in claim 2, is characterized in that described source of iron comprises one or more of ferric phosphate, ferrous oxalate, ferrous acetate, di-iron trioxide, ferric nitrate, ironic citrate etc.
6. preparation method as claimed in claim 2, is characterized in that described phosphorus source comprises one or more in ferric phosphate, phosphorus pentoxide, phosphoric acid, ammonium phosphate, pyrophosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate.
7. preparation method as claimed in claim 2, is characterized in that described dominant carbon source material comprises one or more in glucose, sucrose, polypropylene, polyacrylamide, polyvinyl alcohol, soluble starch, Graphene, citric acid, carbon nano-tube, acetylene black, carbon black.
8. the preparation method as described in claim 2 or 7, is characterized in that the dominant carbon source quality adding is the 25%-60% of lithium source quality; After sintering, the phosphorus content mass percent of LiFePO 4 powder material is between 1.2%-1.8%.
9. preparation method as claimed in claim 2, is characterized in that the addition of tungsten carbide is: every mole of phosphoric acid iron lithium, the quality that adds tungsten carbide is 0.005-0.5g.
10. preparation method as claimed in claim 2, it is characterized in that described ball grinding method is wet ball grinding, blending agent is deionized water, absolute ethyl alcohol, acetone or industrial alcohol, and the ratio of blending agent is the 75%-150% of solid phase gross mass, just to have mobility, is advisable; The incorporation time of liquid phase batch mixing is preferably 4-12 hour; To be mixed evenly and after dry, put into carbon and bury the reducing atmosphere covering and carry out sintering; Be warming up to 350-450 ℃ and carry out pre-burning, heating rate is preferably 1-5 ℃/min, constant temperature time 1-3 hour; Be warming up to 650-750 ℃ and calcine, heating rate is preferably 1-5 ℃/min, constant temperature time 6-12 hour.
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| CN106935840A (en) * | 2017-05-23 | 2017-07-07 | 苏州思创源博电子科技有限公司 | A kind of preparation method of tungsten coated LiFePO 4 for lithium ion batteries positive electrode |
| CN109888277A (en) * | 2019-01-29 | 2019-06-14 | 无锡凯帕德瑞科技有限公司 | The preparation method of positive electrode |
| CN112670485A (en) * | 2020-12-25 | 2021-04-16 | 格林美（无锡）能源材料有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN112670485B (en) * | 2020-12-25 | 2022-08-23 | 格林美(湖北)新能源材料有限公司 | Lithium ion battery anode material and preparation method thereof |
| CN114551880A (en) * | 2021-12-21 | 2022-05-27 | 杭州华宏通信设备有限公司 | Carbon-coated porous Cr-Cu alloy/lithium iron phosphate positive electrode and preparation method thereof |
| CN114551880B (en) * | 2021-12-21 | 2023-07-14 | 杭州华宏通信设备有限公司 | Carbon-coated porous Cr-Cu alloy/lithium iron phosphate anode and preparation method thereof |
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