CN102569796A - Preparation method of lithium iron phosphate/carbon nanotube composite material - Google Patents
Preparation method of lithium iron phosphate/carbon nanotube composite material Download PDFInfo
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Abstract
The invention provides a preparation method of a lithium iron phosphate/carbon nanotube composite material. The preparation method comprises the steps of: dissolving a lithium source and a phosphate source in a mixed liquor agent prepared from alcohol and water to prepare a reaction solution, then adding a ferrous source and a reducing agent, then adding a surfactant, finally adding carbon nanotubes, reacting for 6-8h in a polytetrafluoroethylene high-pressure reaction kettle at 160-200 DEG C to obtain a precursor, calcining the obtained precursor at 600-800 DEG C under the protection of inert gas to prepare the lithium iron phosphate/carbon nanotube composite material with favorable performance. The lithium iron phosphate prepared according to the invention has the advantages of high purity, small grain size, regular shapes and the like, and the carbon nanotubes are embedded into the interiors or cladded onto the surfaces of lithium iron phosphate particles to play a role of electric conductive network, so that the composite material achieves an excellent electrochemical property and is an ideal cathode material for preparing the lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, relate to a kind of preparation method of lithium ion battery anode material lithium iron phosphate/CNT.
Background technology
In in the past 20 years, started the scientific and technological revolution of a field portable electronic product owing to excellent properties such as the specific capacity of lithium ion battery are high, security performance is good.Along with the new-energy automobile industry becomes one of national seven great strategy new industries, as the source of power, battery has become the critical bottleneck of new-energy automobile industry development.And the fast development of lithium ion battery provides technical support for solving this bottleneck.Lithium ion battery also is that sustainable new forms of energy are the most effectively stored and occupation mode simultaneously.Common anode material for lithium-ion batteries adopts LiCoO more at present
2, LiNi
0.8Co
0.15Al
0.05O
2, Li (Mn
1/3Ni
1/3Co
1/3) O
2And LiMn
2O
4Deng material, realized that business-like positive electrode mainly is LiCoO
2Material.Because the resource-constrained of cobalt, cost an arm and a leg and toxic, further limited its commercialization process.Therefore seek a kind of of fine quality, inexpensive, pollution-free, active demand that new type lithium ion battery positive electrode that performance is good has become people.Embedding lithium phosphate anode material for lithium-ion batteries, particularly LiFePO
4Positive electrode relies on the advantage of himself to be shown one's talent, and has won the favor of battery researcher.Its actual capacity can reach 90% of theoretical capacity, is having more advantage aspect cost of material, environmental protection, security performance and the high-power applications, is described as the first-selected reserved materials of lithium ion battery of future generation.But olivine-type LiFePO
4Positive electrode exists three big subject matters: conductivity is low, the lithium ion diffusion coefficient is low, tap density is low.These defectives have then caused its chemical property more undesirable, and then limit its further commercialization and use.In order to overcome above-mentioned defective, the scientific research personnel has carried out numerous researchs, coat and alloying such as carbon, but its effect is more limited.Recently, nano level LiFePO
4Positive electrode has obtained the increasing concern of researcher.Nanoscale LiFePO
4Positive electrode has excellent cycle performance and high-rate charge-discharge capability, and this is because nano particle can shorten the diffusion length and the effective conversion zone of expansion of electronics and lithium ion.Existing nanoscale LiFePO
4The preparation method mainly contain two kinds of hydro thermal method and solvent-thermal methods; Though the granular materials particle diameter of preparing can reach nanoscale, its pattern is rule not really, and distribution of sizes is heterogeneity also; Can not solve the low and low problem of tap density of lithium ion diffusion coefficient effectively, its conductivity is still lower.And when preparing nanoscale LiFePO4 with hydro thermal method or solvent-thermal method, particle surface does not have one deck mechanical protection film in the growth course of particle, can not stop particle further to be assembled, thereby the group's of generation bunch phenomenon.
Summary of the invention
Technical problem:But the invention provides the LiFePO4 of the good LiFePO4 electric conductivity of a kind of chemical property and the preparation method of carbon nano tube compound material,
Technical scheme:The preparation method of LiFePO4 of the present invention and carbon nano tube compound material may further comprise the steps:
1) preparation mixed solvent; Take by weighing following raw material simultaneously, each components contents is a total amount in the molal quantity sum of raw material components: 5 ~ 10% ferrous source, 5 ~ 10% phosphoric acid root, 15 ~ 30% lithium source, 10 ~ 15% reducing agent, 20 ~ 30% surfactant and 20 ~ 30% CNT;
2) said lithium source and phosphoric acid root are mixed to stir with mixed solvent described in the step 1) in container be mixed with the solution that total mol concentration is 0.5 ~ 1.5mol/L, then container is placed in the ultrasonic cleaner solution is carried out the ultrasonic dispersing dissolving;
3) whipping step 2) in the solution that obtains, add ferrous source and reducing agent successively simultaneously, carry out the ultrasonic dispersing dissolving then, thereby obtain the mixed liquor that total mol concentration is 1 ~ 1.5mol/L;
4) surfactant is joined in the mixed liquor that step 3) obtains, carry out the ultrasonic dispersing dissolving then.
5) CNT is joined in the solution that step 4) obtains, it is fully mixed through the ultrasonic dispersing dissolving.
6) with step 5) obtain solution insert in the polytetrafluoroethylene autoclave; React 6 ~ 8h down at 160 ~ 200 ℃; Be cooled to room temperature after the reaction, the product of agitated reactor poured in the funnel of vacuum filtration machine, Yi Bian vacuum filtration; Alternately with deionized water and ethanol cyclic washing, obtain cyan powder on the last filter paper in funnel on one side; Said cyan powder is put into 40 ℃ of following dry 8h of air dry oven, obtain LiFePO4/CNT presoma;
7) LiFePO4 that weighing step 6) obtains/CNT presoma; Be to put into tube furnace after 25 ~ 40% sucrose mixes with it with accounting for above-mentioned LiFePO4/CNT presoma mass percentage content then; Under the protection of inert gas, calcined 6 ~ 10 hours for 600 ~ 800 ℃, obtain LiFePO4/carbon nano tube compound material.
Ferrous source among the present invention is the one or any several kinds combination in frerrous chloride, ferrous acetate, ferrous oxalate, the green vitriol.
Phosphoric acid root among the present invention is the one or any several kinds combination in ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ferric phosphate, the phosphoric acid.
Lithium source among the present invention is the one or any several kinds combination in a hydronium(ion) oxidation lithium, lithium carbonate, lithium nitrate, the lithium dihydrogen phosphate.
Reducing agent among the present invention is the one or any several kinds combination in ascorbic acid, citric acid, the carbonic acid.
Among the present invention, the mixed solvent in the step 1) is any several kinds combination in ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, the deionized water.When being two kinds of liquid combination, each ratio that becomes partial volume is any one of 1:1,1:2; When being three kinds of liquid combination, each composition volume ratio is any one of 1:1:1,1:1:2,1:2:3; When being four kinds of liquid combination, each composition volume ratio is any one of 1:1:1:1,1:1:1:2,1:1:2:3,1:2:3:4.
CNT among the present invention is the one or any several kinds combination in SWCN, double-walled carbon nano-tube, the multi-walled carbon nano-tubes.
Surfactant among the present invention is a polyethylene glycol, the one or any several kinds combination in stearic acid, fatty glyceride, polyvinylpyrrolidone, quaternized thing, the neopelex.
Inert gas among the present invention is the one or any several kinds combination in helium, nitrogen, argon gas, the neon.
Beneficial effect:Existing nanometer LiFePO
4Though the preparation method can synthesize nano level particle, its pattern is rule not really, and distribution of sizes is heterogeneity also; Group's bunch phenomenon be prone to take place, so the inventive method adds surfactant and CNT in its building-up process, can obtain the pattern rule; The nano particle of the less and distribution homogeneous of particle diameter; And make CNT be implanted to granule interior or be coated on the surface, form conductive network, thereby improve the electric conductivity of LiFePO4 widely.
The inventive method is added surfactant in building-up process; In the growth course of particle, be adsorbed on particle surface and stop particle further to assemble or form the micella of definite shape; The effect of control particle diameter and pattern and the generation of prevention group bunch phenomenon have been played; Just can prepare the pattern rule, the nano particle of the littler and distribution homogeneous of particle diameter, the diffusion length that can shorten electronics and lithium ion with enlarge effective conversion zone; Thereby more effectively improved lithium ion diffusion coefficient and tap density, improved its chemical property.
The inventive method adds CNT in building-up process; Perhaps be coated on its surface in the middle of can it being implanted to particle; Just form the very little conductive network of specific insulation; Thereby improve the electric conductivity of LiFePO4 greatly, efficiently solve the low problem of its conductivity, make its charge-discharge performance more excellent.Preparation method of the present invention in addition have technology simply, control easily, advantage such as constant product quality, material property are good.
Description of drawings
Fig. 1 is the X-ray powder diffraction pattern of the LiFePO4/CNT composite material of embodiment 1, embodiment 2 and embodiment 3;
Fig. 2 is the AC impedance figure of the LiFePO4/CNT composite material of embodiment 1, embodiment 2 and embodiment 3;
Fig. 3 is a first charge-discharge curve chart under the 0.1C of LiFePO4/CNT composite material of embodiment 1, embodiment 2 and embodiment 3.
Embodiment
With embodiment method of the present invention is described below, so that the professional and technical personnel more comprehensively understands the present invention, but protection scope of the present invention and execution mode are not limited to the following example.
Lithium source among the present invention can be the one or any several kinds combination in a hydronium(ion) oxidation lithium, lithium carbonate, lithium nitrate, the lithium dihydrogen phosphate.
Ferrous source among the present invention can be the one or any several kinds combination in frerrous chloride, ferrous acetate, ferrous oxalate, the green vitriol.
Phosphoric acid root among the present invention can be the one or any several kinds combination in ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ferric phosphate, the phosphoric acid.
Reducing agent among the present invention can be the one or any several kinds combination in ascorbic acid, citric acid, the carbonic acid.
Mixed solvent in the step 1) of the present invention can be any several kinds combination in ethanol, ethylene glycol, propyl alcohol, isopropyl alcohol, the deionized water.When being two kinds of liquid combination, each ratio that becomes partial volume is any one of 1:1,1:2; When being three kinds of liquid combination, each composition volume ratio is any one of 1:1:1,1:1:2,1:2:3; When being four kinds of liquid combination, each composition volume ratio is any one of 1:1:1:1,1:1:1:2,1:1:2:3,1:2:3:4.
CNT among the present invention can be the one or any several kinds combination in SWCN, double-walled carbon nano-tube, the multi-walled carbon nano-tubes.
Surfactant among the present invention can be a polyethylene glycol, the one or any several kinds combination in stearic acid, fatty glyceride, polyvinylpyrrolidone, quaternized thing, the neopelex.
Embodiment 1:
1) with deionized water and ethylene glycol (V
Water: V
Ethylene glycol=1:1) being mixed with mixed solvent, the mol ratio by 1:1:3:3:6:6 takes by weighing raw material simultaneously: 0.01mol FeSO
47H
2O, 0.01mol H
3PO
4, 0.03mol LiOHH
2O, 0.03mol citric acid, 0.06mol polyvinylpyrrolidone K-30 (polyvinylpyrrolidone, PVP) or the low molecule of polyethylene glycol-400 (polyethylene glycol is PEG-400) with 0.06mol SWCN (CNT);
2) get the mixed solvent 60ml for preparing in the step 1), at first with LiOHH
2O and H
3PO
4In beaker, mix stirring and be mixed with the solution that total mol concentration is 0.67mol/L, then beaker is placed in the ultrasonic cleaner solution is carried out the ultrasonic dispersing dissolving with mixed solvent;
3) with step 2) in the solution that obtains add FeSO while stirring successively
47H
2O and citric acid carry out the ultrasonic dispersing dissolving then, thereby obtain the mixed liquor of total mol concentration 1.33mol/L;
4) with surfactant polyvinylpyrrolidone K-30 macromolecule (polyvinylpyrrolidone; PVP) or low molecule (the polyethylene glycol of polyethylene glycol-400; PEG-400), join in the mixed liquor that obtains in the step 3) ultrasonic dispersing dissolving then;
5) SWCN (CNT) is joined in the solution that obtains in the step 4), it is fully mixed through the ultrasonic dispersing dissolving;
6) with obtain in the step 5) solution insert polytetrafluoroethylene (PTFE; Poly tetra fluoro ethylene ptfe) reacts 6 ~ 8h down at 160 ~ 200 ℃ in the autoclave; Be cooled to room temperature after the reaction, the product of agitated reactor poured in the funnel of vacuum filtration machine, Yi Bian vacuum filtration; On one side alternately with deionized water and ethanol cyclic washing; Obtain cyan powder on the last filter paper in funnel, said cyan powder is put into 40 ℃ of following dry 8h of air dry oven, obtain LiFePO4/CNT presoma;
7) LiFePO4 that step 6) is obtained/CNT presoma is to put into tube furnace after 25% sucrose mixes with accounting for above-mentioned presoma mass percentage content, in the tube furnace device, feeds nitrogen, at N
2Protection under 600 ~ 800 ℃ the calcining 6 ~ 10 hours, just obtain LiFePO4/carbon nano tube compound material.
Adopt XPert Pro MPD type x-ray diffractometer (the CuK α of Philips
1, λ=0.1544nm, it is 40 kV that pipe is pressed, Guan Liuwei 40 mA) sample that obtains is carried out material phase analysis.
With the LiFePO that obtains
4/ CNT sample and acetylene black, PVDF mix according to mass ratio 80:12:8; Make the uniform slurry of solvent furnishing with the N-methyl pyrrolidone; It is coated on the aluminium foil disk that diameter is 1cm equably; Then 100 ℃ dry 24 hours down, dry back with the powder hydraulic press with positive plate compacting under 20MPa.Adopting the lithium sheet is negative pole, and the Celgard2300 microporous polypropylene membrane is a barrier film, the LiPF of 1.0 mol/ L
6/ EC+DMC (1:1) is an electrolyte, under nitrogen protection, is assembled into CR2032 type battery in the Vigor VG1200/750TS vacuum glove box.Survey its performance with LAND charge-discharge test appearance, charge-discharge magnification is 0.1C, and the charging/discharging voltage scope is 2.0V-4.2V; Test its AC impedance with occasion China CHI660D electrochemical workstation.Show LiFePO through XRD analysis
4Be pure phase, and crystallinity is better, as shown in Figure 1.Fig. 2 has provided the AC impedance figure of this composite material, and the size of high frequency region arc radius means the resistance sizes between the material granule, and it is less from figure, can to analyze the resistance that draws between this material granule, and its cycle performance is better.Visible by Fig. 3, under the 0.1C multiplying power, mild charge and discharge platform has appearred in curve about 3.4V, approach LiFePO
4The theoretical value of particle platform voltage (3.45V), and the difference of charge and discharge platform voltage is very little, and the dynamic performance of illustrative material is good.First discharge specific capacity reaches 157.1 mAh.g
-1, approach LiFePO
4Theoretical specific capacity (169 mAh.g
-1), explain that (polyethylene glycol PEG-400) has improved the discharge performance of material to the low molecules of PVP macromolecule or polyethylene glycol-400 with the interpolation of CNT.
Embodiment 2: with deionized water and ethylene glycol (V
Water: V
Ethylene glycol=1:1) being mixed with mixed solvent, the mol ratio by 1:1:3:5/3:10/3:10/3 takes by weighing raw material simultaneously: 0.01mol FeSO
47H
2O, 0.01mol H
3PO
4, 0.03mol LiOHH
2O, 0.0167mol citric acid, 0.033mol polyvinylpyrrolidone K-30 (polyvinylpyrrolidone, PVP) or the low molecule of polyethylene glycol-400 (polyethylene glycol is PEG-400) with 0.033mol SWCN (CNT); Step 2) lithium source in and phosphoric acid root obtain solution concentration are 0.5mol/L, and the solution concentration in the step 3) behind adding ferrous source and the reducing agent is 1.5mol/L, and the sucrose addition is 37% for accounting for the presoma mass percent in the step 7).
Consistent among synthetic other steps, electrode making, battery assembling, characterization technique, test condition with preparation of material and the embodiment 1.
Show LiFePO through XRD analysis
4Be pure phase, and crystallinity is better, as shown in Figure 1.AC impedance figure and example 1, example 3 that Fig. 2 has provided this composite material contrast the arc radius size of high frequency region down, and it is maximum can analyzing the resistance that draws between this material granule, and its cycle performance also is the poorest.Visible by Fig. 3, under the 0.1C multiplying power, mild charge and discharge platform has appearred in curve about 3.4V, approach LiFePO
4The theoretical value of particle platform voltage (3.45V), and the difference of charge and discharge platform voltage is very little, and the dynamic performance of illustrative material is good.First discharge specific capacity reaches 147.6 mAh.g-1, approaches LiFePO
4Theoretical specific capacity (169 mAh.g-1), but do not have the specific capacity of embodiment 1 high.
Embodiment 3: with deionized water and ethylene glycol (V
Water: V
Ethylene glycol=1:1) being mixed with mixed solvent, the mol ratio by 1:1:3:1:2:2 takes by weighing raw material simultaneously: 0.01mol FeSO
47H
2O, 0.01mol H
3PO
4, 0.03mol LiOHH
2O, 0.01mol citric acid, 0.02mol polyvinylpyrrolidone K-30 (polyvinylpyrrolidone, PVP) or the low molecule of polyethylene glycol-400 (polyethylene glycol is PEG-400) with 0.02mol SWCN (CNT); Step 2) lithium source in and phosphoric acid root obtain solution concentration are 1.5mol/L, and the solution concentration in the step 3) behind adding ferrous source and the reducing agent is 1mol/L, and the sucrose addition is 40% for accounting for the presoma mass percent in the step 7).
Consistent among synthetic other steps, electrode making, battery assembling, characterization technique, test condition with preparation of material and the embodiment 1.
Show LiFePO through XRD analysis
4Be pure phase, and crystallinity is better, as shown in Figure 1.AC impedance figure and example 1, example 2 that Fig. 2 has provided this composite material contrast the arc radius size of high frequency region down, and it is minimum can analyzing the resistance that draws between this material granule, and its cycle performance ratio 1 all will be got well with example 2.Visible by Fig. 3, under the 0.1C multiplying power, mild charge and discharge platform has appearred in curve about 3.4V, approach LiFePO
4The theoretical value of particle platform voltage (3.45V), and the difference of charge and discharge platform voltage is very little, and the dynamic performance of illustrative material is good.First discharge specific capacity reaches 131.6 mAh.g-1, relatively approaches LiFePO
4Theoretical specific capacity (169 mAh.g-1), but all do not have example 1 high with example 2 specific capacity.
Embodiment 4: ferrous source adopts frerrous chloride, and the phosphoric acid root adopts ammonium dihydrogen phosphate, and lithium nitrate is adopted in the lithium source, and reducing agent adopts ascorbic acid, and surfactant adopts stearic acid, and CNT adopts double-walled carbon nano-tube, and other are with embodiment 1.
Embodiment 5: ferrous source adopts ferrous acetate, and the phosphoric acid root adopts ammonium hydrogen phosphate, and lithium carbonate and lithium nitrate are adopted in the lithium source; Reducing agent adopts carbonic acid and citric acid; Surfactant adopts fatty glyceride and polyvinylpyrrolidone, and CNT adopts multi-walled carbon nano-tubes, and other are with embodiment 1.
Embodiment 6: ferrous source adopts frerrous chloride and ferrous oxalate, and the phosphoric acid root adopts ferric phosphate, and LiOHH is adopted in the lithium source
2O and lithium dihydrogen phosphate, reducing agent adopts ascorbic acid and citric acid, and surfactant adopts quaternized thing and neopelex, and CNT adopts the combination of SWCN, double-walled carbon nano-tube and multi-walled carbon nano-tubes, and other are with embodiment 2.
Embodiment 7: ferrous source adopts ferrous oxalate; The phosphoric acid root adopts ammonium dihydrogen phosphate; Lithium nitrate is adopted in the lithium source, and reducing agent adopts ascorbic acid, citric acid and carbonic acid, and surfactant adopts the combination of polyethylene glycol, fatty glyceride and polyvinylpyrrolidone; CNT adopts the combination of SWCN and multi-walled carbon nano-tubes, and other are with embodiment 2.
Embodiment 8: ferrous source adopts ferrous acetate and FeSO
47H
2O, the phosphoric acid root adopts ammonium dihydrogen phosphate and phosphoric acid, and lithium carbonate and lithium dihydrogen phosphate are adopted in the lithium source, and reducing agent adopts ascorbic acid and carbonic acid, and surfactant adopts stearic acid and quaternized thing, and CNT adopts multi-walled carbon nano-tubes, and other are with embodiment 3.
Embodiment 9: ferrous source adopts ferrous acetate, ferrous oxalate and FeSO
47H
2O, the phosphoric acid root adopts ammonium hydrogen phosphate and phosphoric acid, and LiOHH is adopted in the lithium source
2O and lithium nitrate, reducing agent adopts the combination of ascorbic acid and carbonic acid, and surfactant adopts the combination of stearic acid and polyvinylpyrrolidone, and CNT adopts double-walled carbon nano-tube, and other are with embodiment 3.
Claims (9)
1. the preparation method of LiFePO4 and carbon nano tube compound material is characterized in that this method may further comprise the steps:
1) preparation mixed solvent; Take by weighing following raw material simultaneously, each components contents is a total amount in the molal quantity sum of raw material components: 5 ~ 10% ferrous source, 5 ~ 10% phosphoric acid root, 15 ~ 30% lithium source, 10 ~ 15% reducing agent, 20 ~ 30% surfactant and 20 ~ 30% CNT;
2) said lithium source and phosphoric acid root are mixed to stir with mixed solvent described in the step 1) in container be mixed with the solution that total mol concentration is 0.5 ~ 1.5mol/L, then container is placed in the ultrasonic cleaner solution is carried out the ultrasonic dispersing dissolving;
3) whipping step 2) in the solution that obtains, add ferrous source and reducing agent successively simultaneously, carry out the ultrasonic dispersing dissolving then, thereby obtain the mixed liquor that total mol concentration is 1 ~ 1.5mol/L;
4) surfactant is joined in the mixed liquor that step 3) obtains, carry out the ultrasonic dispersing dissolving then;
5) CNT is joined in the solution that step 4) obtains, it is fully mixed through the ultrasonic dispersing dissolving;
6) with step 5) obtain solution insert in the polytetrafluoroethylene autoclave; React 6 ~ 8h down at 160 ~ 200 ℃; Be cooled to room temperature after the reaction, the product of agitated reactor poured in the funnel of vacuum filtration machine, Yi Bian vacuum filtration; Alternately with deionized water and ethanol cyclic washing, obtain cyan powder on the last filter paper in funnel on one side; Said cyan powder is put into 40 ℃ of following dry 8h of air dry oven, obtain LiFePO4/CNT presoma;
The quality of the LiFePO4 that 7) weighing step 6) obtains/CNT presoma; Be to put into tube furnace after 25 ~ 40% sucrose mixes with it with accounting for said LiFePO4/CNT presoma mass percentage content then; Under the protection of inert gas, calcined 6 ~ 10 hours for 600 ~ 800 ℃, obtain LiFePO4/carbon nano tube compound material.
2. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material is characterized in that, described ferrous source is the one or any several kinds combination in frerrous chloride, ferrous acetate, ferrous oxalate, the green vitriol.
3. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material is characterized in that, described phosphoric acid root is the one or any several kinds combination in ammonium dihydrogen phosphate, ammonium hydrogen phosphate, ferric phosphate, the phosphoric acid.
4. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material is characterized in that, described lithium source is the one or any several kinds combination in a hydronium(ion) oxidation lithium, lithium carbonate, lithium nitrate, the lithium dihydrogen phosphate.
5. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material is characterized in that, described reducing agent is the one or any several kinds combination in ascorbic acid, citric acid, the carbonic acid.
6. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material is characterized in that, the mixed solvent in the said step 1) is any several kinds combination in ethanol, ethylene glycol, isopropyl alcohol, the deionized water; When being two kinds of liquid combination, each composition volume ratio is any one of 1:1,1:2; When being three kinds of liquid combination, each composition volume ratio is any one of 1:1:1,1:1:2,1:2:3; When being four kinds of liquid combination, each composition volume ratio is any one of 1:1:1:1,1:1:1:2,1:1:2:3,1:2:3:4.
7. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material; It is characterized in that; Described surfactant is a polyethylene glycol, the one or any several kinds combination in stearic acid, fatty glyceride, polyvinylpyrrolidone, quaternized thing, the neopelex.
8. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material is characterized in that, described CNT is the one or any several kinds combination in SWCN, double-walled carbon nano-tube, the multi-walled carbon nano-tubes.
9. the preparation method of LiFePO4 according to claim 1 and carbon nano tube compound material is characterized in that, described inert gas is the one or any several kinds combination in helium, nitrogen, argon gas, the neon.
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| CN109037658A (en) * | 2018-08-31 | 2018-12-18 | 重庆工商大学 | A kind of lithium iron phosphate positive material preparation method of polymer overmold |
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| CN109786699A (en) * | 2018-12-29 | 2019-05-21 | 合肥融捷能源材料有限公司 | A kind of high-compaction lithium iron phosphate anode and its hydro-thermal method preparation method |
| CN114835102A (en) * | 2022-07-01 | 2022-08-02 | 北京理工大学深圳汽车研究院(电动车辆国家工程实验室深圳研究院) | Method for regenerating lithium iron phosphate based on solvothermal method |
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