CN107093732B - A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery - Google Patents
A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery Download PDFInfo
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Abstract
The present invention relates to a kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation methods for anode material of lithium battery, the composite material is made of LiFePO4 core and carbon nanotube shell, it specifically prepares by the following method: ferric lithium phosphate precursor and catalyst precursor is stirred in a solvent, and pH value is adjusted with alkali, it is added in hydrothermal reaction kettle and is warming up to 500 DEG C of reaction 12h, catalyst is made and loads LiFePO4 slurry；Then catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, gaseous carbon sources, which are catalyzed, under high temperature and inert gas is coated on LiFePO4 surface for carbon nanotube, obtains lithium iron phosphate/carbon nano-tube nano composite material.The chemical properties such as material electric conductivity with higher, specific capacity and multiplying power property, can be widely used for the positive electrode of electric vehicle lithium battery, cellular li-ion battery etc..
Description
Technical field
The present invention relates to a kind of anode material of lithium battery more particularly to a kind of ferric phosphates for anode material of lithium battery
Lithium/carbon nanotube composite materials and preparation method thereof.
Background technique
The LiFePO4 of olivine-type is because its raw material sources is abundant, price is cheap, thermal stability is good, and cycle performance is excellent etc.
Advantage is considered as a kind of Olivine-type Cathode Material in Li-ion Batteries with broad prospect of application, and is applied to power battery or storage
It can battery.And the raising with people to electric car, mobile phone fast charge demand, lithium ion battery need to have higher multiplying power, mesh
It is preceding to be difficult to realize because LiFePO4 conductivity is lower.
For the electric conductivity for improving LiFePO4, carbon-coated method is widely used at present, on the one hand can improve ferric phosphate
The electric conductivity of lithium, while growing up for LiFePO4 crystal grain can be prevented under the conditions of solid phase high―temperature nuclei, it is conducive to nano-scale powder
Preparation, to realize the high magnification of lithium ion battery.Chinese patent CN101636861A, US2010/0297496A1 and
CN1186835C adds carbon source presoma reheating solution into ferric lithium phosphate precursor using the method for physical mixed and forms carbon coating
Layer, but pyrolysis carbon material electric conductivity due to crystallinity difference itself is bad, phosphorus can be reduced by increasing raising electric conductivity by carbon content
The chemical property of sour iron lithium.
Chinese patent CN101442126A and CN101533904A are introducing catalytic component using chemical vapour deposition technique
The step of doping, generates carbon nanotube, but the physics mode of ball milling mixing is difficult to ensure that catalyst is uniformly distributed, and fixed bed
Chemical gaseous phase deposition also causes nano-carbon layer deposition uneven.In addition, this method will can make when introducing catalyst with water and oxygen, water
Lithium in LiFePO4 generates LiOH and Li2CO3, oxygen can be such that LiFePO4 aoxidizes, to generate negative shadow to LiFePO4
It rings.The ferric lithium phosphate precursor powder, catalyst and the liquid carbon source that prepare are uniformly mixed by Chinese patent CN102427130B
Slurry is made, by feeding to high temperature reaction stove by spraying, generates lithium iron phosphate/carbon nano tube compound material, this method exists
Following problems: 1. liquid carbon source just facilitates under higher content enters reacting furnace by spraying, and liquid carbon source is because cannot be with catalyst
It comes into full contact with and is easy to generate carbon coating layer and non-carbonic nanotube, the electric conductivity of carbon can not show a candle to carbon nanotube, to influence ferric phosphate
The chemical property of lithium；2. simply ferric lithium phosphate precursor powder, catalyst and liquid carbon source physical blending are difficult to realize
To effective cladding of LiFePO4, carbon or carbon nanotube are possible in a free form the carbon or carbon nanotube that liquid carbon source generates
In the presence of exposed LiFePO4 affects the promotion of electrochemical performances of lithium iron phosphate because electric conductivity is not good enough.
From the foregoing, it will be observed that current lithium iron phosphate/carbon nano-tube nano composite material has the disadvantage in that 1. catalyst and carbon
Source contact is uneven, and the carbon generated is caused to increase, electric conductivity decline, to influence the chemical property of material；2. introducing catalysis
When agent, bring water can make the lithium in LiFePO4 generate LiOH and Li2CO3, bring oxygen can be such that LiFePO4 aoxidizes,
To have a negative impact to LiFePO4；3. liquid carbon source with catalyst due to cannot come into full contact with easy generation carbon coating layer
The electric conductivity of non-carbonic nanotube, carbon can not show a candle to carbon nanotube, to influence the chemical property of LiFePO4；4. carbon or carbon nanometer
Pipe is possible to exist in a free form, and exposed LiFePO4 affects electrochemical performances of lithium iron phosphate because electric conductivity is not good enough
It is promoted.
Summary of the invention
The object of the present invention is to provide a kind of lithium iron phosphate/carbon nano-tube nano composite material of anode material of lithium battery and
Preparation method, contacts that uneven, carbon nanotube transformation efficiency is low, can bring when introducing catalyst to solve catalyst with carbon source
Water and oxygen, carbon nanotube coat incomplete and non-uniform problem, effectively improve lithium iron phosphate/carbon nano-tube nano composite wood
The chemical properties such as electric conductivity, specific capacity and the multiplying power property of material.
In order to solve the above technical problems, the present invention provides a kind of lithium iron phosphate/carbon nanometer for anode material of lithium battery
Pipe nanocomposite, the composite material are made of LiFePO4 core and carbon nanotube shell, and wherein lithium iron phosphate particles are olive
Stone structure, aggregate particle size are 0.2 micron -10 microns；The carbon nanotube is wrapped in LiFePO4 surface, the pipe of carbon nanotube
Diameter is 2 nanometers -20 nanometers, and the internal diameter of carbon nanotube is 1 nanometer -10 nanometers, and the length of the carbon nanotube is 100 nanometer -1000
Nanometer.
The core-shell structure of lithium iron phosphate/carbon nanotube realizes carbon nanotube to the cladding of LiFePO4, improves it and leads
Electrical property and chemical property.In addition, the size of LiFePO4 and carbon nanotube affects the performance of material: LiFePO4 partial size mistake
Conference coat carbon nanotube can not completely, and partial size is too small and the easy reunion of LiFePO4 is caused to be difficult to disperse to influence uniformly
Cladding；Carbon nanotube is slightly difficult to very much coat up, too thin to be difficult to coat completely with too short, too long to be easy to be free in LiFePO4
Surface all influences the effect of cladding.
Preferably, the aggregate particle size of the lithium iron phosphate particles is 0.5 micron -5 microns, and the pipe of the carbon nanotube
Diameter is 3 nanometers -10 nanometers, and internal diameter is 2 nanometers -6 nanometers, and the length of carbon nanotube is 200 nanometers -800 nanometers.
Preferably, the aggregate particle size of the lithium iron phosphate particles is 1 micron -3 microns, and the caliber of the carbon nanotube
It is 4 nanometers -6 nanometers, internal diameter is 3 nanometers -5 nanometers, and the length of carbon nanotube is 400 nanometers -600 nanometers.
Realize that above-mentioned purpose, the present invention provide a kind of manufacture aforementioned phosphate iron lithium/carbon nanotube composite materials system
Preparation Method includes the following steps:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 2%-20%, the molar content of molybdenum is 2%-15%, magnesium
Molar content is 25%-90%,；Each component is stirred in a solvent, and adjusts pH value with alkali, is then added to water
It is warming up to 300 DEG C of -800 DEG C of reaction 1h-24h in thermal response kettle, catalyst is made and loads LiFePO4 slurry；
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above chemical vapor depsotition equipment (CVD) by spraying apparatus,
Size droplet diameter after atomization is 1 micron -100 microns, and the drop after atomization enters high temperature reaction zone, and temperature is 600 DEG C -700 DEG C,
Make carrier gas using indifferent gas and is passed through one or more of hydrogen, nitrogen, methane, ethyl alcohol, acetylene, ethylene below CVD as carbon
The flow that is passed through in source, carbon source is 200SCCM-4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is in CVD high temperature
Area residence time 2h-8h, the reaction time of CVD process is controlled by high pressure draught obtains phosphoric acid below 20s-20min, CVD
Iron lithium/carbon nanotube composite materials.
During the reaction, atomized drop is too small, and spraying apparatus cannot achieve；Atomized drop is excessive, the ferric phosphate of generation
Lithium particle is excessive, to influence the cladding of carbon nanotube.Meanwhile reaction temperature is too low, the reaction time is too short, is unfavorable for the shadow that is carbonized
Ring the generation of carbon nanotube；Reaction temperature is excessively high, the reaction time is too long, and energy consumption is excessive.It is unfavorable in addition, the flow of carbon source is too fast
The generation and cladding of carbon nanotube, flow influence production efficiency slowly excessively.
As optimization design, the ferric lithium phosphate precursor salt is divided into lithium source, source of iron and phosphorus source three classes, and wherein lithium source is
At least one of Li source compounds such as lithium hydroxide, lithium carbonate, lithium phosphate, lithium oxalate, lithium acetate；Source of iron is three oxidations two
At least one of iron, ferroso-ferric oxide, ferric phosphate, ferrous phosphate, ferrous oxalate, ferrous sulfate；Phosphorus source is phosphoric acid, di(2-ethylhexyl)phosphate
Any one in the P source compounds such as hydrogen ammonium, diammonium hydrogen phosphate, ammonium phosphate, ferric phosphate.
As optimization design, the solvent is at least one of dehydrated alcohol, methanol, acetone, propyl alcohol, is born with catalyst
The solid-to-liquid ratio for carrying ferric lithium phosphate precursor is 6%-65%；The precursor material of the catalyst is divided into iron, nickel, molybdenum, four class of magnesium,
Specially oxide, hydroxide, halide, sulfate, carbonate, nitrate, phosphate, acetate, oxalates, fatty acid
At least one of salt, Metallocenic compound, metal carbonyl.
As optimization design, the alkali be at least one of ammonia, urea, sodium carbonate, sodium bicarbonate, ammonium hydrogen carbonate, and
Mass percent shared by the catalytic component is 0.6%-4%；The CVD refers to chemical vapor deposition process and its improves enhancing
Technique, including CVD, PECVD, LPCVD, HPD-CVD, HFCVD, microwave plasma enhancing chemical vapor deposition process in one
Kind；The inert atmosphere includes at least one of nitrogen, argon gas, helium.
As optimization design, iron in the step (1), nickel molar content be 5-15%, and the molar content of molybdenum is
4%-12%, the molar content of magnesium are 40%-85%；And the size droplet diameter after step (2) atomization is 5 microns -20 microns,
It is 600 DEG C -700 DEG C that drop after atomization, which enters high temperature reaction zone temperature, and the flow that is passed through of carbon source is 500SCCM-
2000SCCM, and controlling catalyst load ferric lithium phosphate precursor slurry in the high-temperature region CVD residence time is 3h-6h.
As optimization design, iron in the step (1), nickel molar content be 8-13%, and the molar content of molybdenum is
8%-12%, the molar content of magnesium are 75%-82%；And the size droplet diameter after step (2) atomization is 8 microns -12 microns,
It is 650 DEG C -680 DEG C that drop after atomization, which enters high temperature reaction zone temperature, and the flow that is passed through of carbon source is 800SCCM-
1000SCCM, and controlling catalyst load ferric lithium phosphate precursor slurry in the high-temperature region CVD residence time is 4h-5h.
Lithium iron phosphate/carbon nano-tube nano composite material of the invention has the advantage that
1. the present invention is that carbon nanotube is shell, LiFePO4 is the nanocomposite of core, and carbon nanotube is to LiFePO4
Complete cladding, avoid the exposed of insulating properties LiFePO4, improve the electric conductivity of material；
2. the hydro-thermal reaction in the present invention is conducive to generate the catalyst uniform load LiFePO4 of Nano grade, make to be catalyzed
Agent can come into full contact on the surface of LiFePO4 with carbon source, not only make the high conversion rate of carbon nanotube, but also carbon nanotube is to phosphorus
The cladding of sour iron lithium is spent completely and the uniformity is high, to improve the electric conductivity of LiFePO4；
3. the present invention can not only be come into full contact with using gas as carbon source with catalyst and LiFePO4, and can be kept away
The generation for exempting from carbon, improves the conversion ratio of carbon nanotube, to improve the electric conductivity of LiFePO4；
4. entire CVD technique of the invention uses inert gas, oxygen is avoided, moisture receives lithium iron phosphate/carbon nanotube
The negative effect of nano composite material.
Specific embodiment
The present invention discloses a kind of lithium iron phosphate/carbon nano-tube nano composite material for anode material of lithium battery, this is multiple
Condensation material is made of LiFePO4 core and carbon nanotube shell, in which: lithium iron phosphate particles are olivine structural, and aggregate particle size is
0.2 micron -10 microns, preferably 0.5 micron -5 microns, more preferable 1 micron -3 microns, LiFePO4 partial size, which crosses conference, makes carbon nanometer
Pipe can not be coated completely, and partial size is too small and the easy reunion of LiFePO4 is caused to be difficult to disperse to influence uniformly to coat.Carbon nanometer
Pipe is wrapped in the surface of LiFePO4, and the caliber of carbon nanotube is 2 nanometers -20 nanometers, and preferably 3 nanometers -10 nanometers, more preferable 3
- 6 nanometers of nanometer, internal diameter are 1 nanometer -10 nanometers, and preferably 2 nanometers -6 nanometers, more preferable 3 nanometers -5 nanometers, length is received for 100
Rice -1000 nanometers, preferably 200 nanometers -800 nanometers, more preferable 400 nanometers -600 nanometers, the carbon nanotube of suitable dimension all without
Method is realized to the complete cladding of LiFePO4, is slightly difficult to very much coat up, too thin to be difficult to coat too long easy trip completely with too short
From the effect on the surface of LiFePO4, all influencing cladding.
Invention additionally discloses a kind of lithium iron phosphate/carbon nano-tube nano composite materials for manufacturing aforementioned anode material of lithium battery
Preparation method, include the following steps:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 2%-20%, the molar content of molybdenum is 2%-15%, magnesium
Molar content is 25%-90%,；Each component is stirred in a solvent, and adjusts pH value with alkali, is then added to water
It is warming up to 300 DEG C of -800 DEG C of reaction 1h-24h in thermal response kettle, catalyst is made and loads LiFePO4 slurry；
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above chemical vapor depsotition equipment (CVD) by spraying apparatus,
Size droplet diameter after atomization is 1 micron -100 microns, and the drop after atomization enters high temperature reaction zone, and temperature is 600 DEG C -700 DEG C,
Make carrier gas using indifferent gas and is passed through one or more of hydrogen, nitrogen, methane, ethyl alcohol, acetylene, ethylene below CVD as carbon
The flow that is passed through in source, carbon source is 200SCCM-4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is in CVD high temperature
Area residence time 2h-8h, the reaction time of CVD process is controlled by high pressure draught obtains phosphoric acid below 20s-20min, CVD
Iron lithium/carbon nanotube composite materials.
Ferric lithium phosphate precursor salt is divided into lithium source, source of iron and phosphorus source three classes, wherein lithium source be lithium hydroxide, lithium carbonate,
At least one of Li source compounds such as lithium phosphate, lithium oxalate, lithium acetate；Source of iron is di-iron trioxide, ferroso-ferric oxide, phosphoric acid
At least one of iron, ferrous phosphate, ferrous oxalate, ferrous sulfate；Phosphorus source is phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus
Any one in the P source compounds such as sour ammonium, ferric phosphate.
Solvent is at least one of dehydrated alcohol, methanol, acetone, propyl alcohol, loads ferric lithium phosphate precursor with catalyst
Solid-to-liquid ratio be 6%-65%；The precursor material of catalyst is divided into iron, nickel, molybdenum, four class of magnesium, specially oxide, hydroxide
Object, halide, sulfate, carbonate, nitrate, phosphate, acetate, oxalates, fatty acid salt, Metallocenic compound, gold
Belong at least one of carbonyls.
Alkali is at least one of ammonia, urea, sodium carbonate, sodium bicarbonate, ammonium hydrogen carbonate, and quality shared by catalytic component
Percentage is 0.6%-4%；CVD refer to chemical vapor deposition process and its improve enhancing technique, including CVD, PECVD,
One of LPCVD, HPD-CVD, HFCVD, microwave plasma enhancing chemical vapor deposition process；Inert atmosphere include nitrogen,
At least one of argon gas, helium.
Iron in step (1), nickel molar content be 5-15%, and the molar content of molybdenum is 4%-12%, and magnesium mole contains
Amount is 40%-85%；And the size droplet diameter after step (2) atomization is 5 microns -20 microns, it is anti-that the drop after atomization enters high temperature
Answering area's temperature is 600 DEG C -700 DEG C, and the flow that is passed through of carbon source is 500SCCM-2000SCCM, and controls catalyst and load phosphoric acid
Iron lithium precursor pulp is 3h-6h in the high-temperature region CVD residence time.
Iron in step (1), nickel molar content be 8-13%, and the molar content of molybdenum is 8%-12%, and magnesium mole contains
Amount is 75%-82%；And the size droplet diameter after step (2) atomization is 8 microns -12 microns, it is anti-that the drop after atomization enters high temperature
Answering area's temperature is 650 DEG C -680 DEG C, and the flow that is passed through of carbon source is 800SCCM-1000SCCM, and controls catalyst and load phosphoric acid
Iron lithium precursor pulp is 4h-5h in the high-temperature region CVD residence time.
After the preparation of lithium iron phosphate/carbon nano-tube nano pipe nanocomposite, button half-cell is made as follows
And test specific capacity and multiplying power property: lithium iron phosphate/carbon nanotube and PVDF being weighed with the mass ratio of 90:10, after mixed pulp
Film, drying, compacting, punching, a pour lithium slice is cathode in vacuum glove box, to be dissolved in volume ratio as the carbonic acid second of 1:1
Lithium hexafluoro phosphate in ester and methyl carbonate is electrolyte, and polypropylene microporous film is diaphragm, forms 2032 button cells, and adopt
Carry out constant current constant voltage charge-discharge test with new prestige battery controlled testing instrument, by voltage be 4.2V-2.0V.
Embodiment 1:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 13%, the molar content of molybdenum is 12%, the molar content of magnesium
It is 75%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 800 DEG C of reaction 1h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is 1
Micron, the drop after atomization enter high temperature reaction zone, and temperature is 600 DEG C, make carrier gas with indifferent gas and are passed through ethyl alcohol work below CVD
For carbon source, being passed through flow is 4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is when the high-temperature region CVD stops
Between 8h, obtain lithium iron phosphate/carbon nano-tube nano composite material below CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 135mAh/g after 30 weeks,
Discharging efficiency is maintained at 97% or more, has excellent multiplying power property.
Embodiment 2:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 8%, the molar content of molybdenum is 10%, and the molar content of magnesium is
82%, each component is stirred, and adjust pH value with alkali in a solvent, is then added in hydrothermal reaction kettle and is warming up to
300 DEG C of reactions for 24 hours, are made catalyst and load LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
100 microns, the drop after atomization enters high temperature reaction zone, and temperature is 700 DEG C, makees carrier gas with indifferent gas and is passed through hydrogen below CVD
For gas as carbon source, being passed through flow is 200SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Time 2h, obtain lithium iron phosphate/carbon nano-tube nano composite material below CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 140mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Embodiment 3:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 10%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 80%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 600 DEG C of reaction 10h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
10 microns, the drop after atomization enters high temperature reaction zone, and temperature is 660 DEG C, makees carrier gas with indifferent gas and is passed through methane below CVD
As carbon source, being passed through flow is 1000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 4h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 145mAh/g after 30 weeks,
Discharging efficiency is maintained at 99% or more, has excellent multiplying power property.
Embodiment 4:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 8%, the molar content of molybdenum is 11%, and the molar content of magnesium is
81%, each component is stirred, and adjust pH value with alkali in a solvent, is then added in hydrothermal reaction kettle and is warming up to
500 DEG C of reaction 12h are made catalyst and load LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
11 microns, the drop after atomization enters high temperature reaction zone, and temperature is 670 DEG C, makees carrier gas with indifferent gas and is passed through methane below CVD
As carbon source, being passed through flow is 900SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 5h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 142mAh/g after 30 weeks,
Discharging efficiency is maintained at 99% or more, has excellent multiplying power property.
Embodiment 5:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 12%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 78%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 500 DEG C of reaction 12h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
11 microns, the drop after atomization enters high temperature reaction zone, and temperature is 670 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 1000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 4h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 149mAh/g after 30 weeks,
Discharging efficiency is maintained at 99% or more, has excellent multiplying power property.
Embodiment 6:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 18%, the molar content of molybdenum is 12%, the molar content of magnesium
It is 70%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 600 DEG C of reaction 8h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
20 microns, the drop after atomization enters high temperature reaction zone, and temperature is 660 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 2000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 3h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 156mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Embodiment 7:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 10%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 80%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 700 DEG C of reaction 4h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
20 microns, the drop after atomization enters high temperature reaction zone, and temperature is 700 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 1800SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 4h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 153mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Embodiment 8:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, at the same be added iron, nickel, molybdenum, in magnesium salts
One or more catalyst precursors, iron, nickel molar content be 10%, the molar content of molybdenum is 10%, the molar content of magnesium
It is 80%, each component is stirred in a solvent, and adjust pH value with alkali, is then added in hydrothermal reaction kettle and heats up
To 600 DEG C of reaction 8h, catalyst is made and loads LiFePO4 slurry.
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above CVD by spraying apparatus, the size droplet diameter after atomization is
20 microns, the drop after atomization enters high temperature reaction zone, and temperature is 660 DEG C, makees carrier gas with indifferent gas and is passed through ethylene below CVD
As carbon source, being passed through flow is 2000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is stopped in the high-temperature region CVD
Lithium iron phosphate/carbon nano-tube nano composite material is obtained below time 3h, CVD.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 156mAh/g after 30 weeks,
Discharging efficiency is maintained at 98% or more, has excellent multiplying power property.
Comparative example 1:
Referring to embodiment 3, LiFePO4 is directly mixed with carbon nanotube.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 105mAh/g after 30 weeks,
Discharging efficiency is maintained at 82% or less.
Comparative example 2:
Referring to embodiment 3, changes gaseous carbon source into liquid carbon source, obtain lithium iron phosphate/carbon nano tube compound material.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 115mAh/g after 30 weeks,
Discharging efficiency is maintained at 83% or less.
Comparative example 3:
Referring to embodiment 3, hydro-thermal reaction is removed, lithium iron phosphate/carbon nano tube compound material is obtained.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity to reach 108mAh/g after 30 weeks,
Discharging efficiency is maintained at 82% or less.
Comparative example 4:
Referring to embodiment 3, changes inert gas into oxygen and vapor, obtain lithium iron phosphate/carbon nano tube compound material.
Charge-discharge test under 6C multiplying power is carried out using the material, circulation still keeps discharge capacity up to 68mAh/g, puts after 30 weeks
Electrical efficiency is maintained at 57% or less.
It is to be provided for the embodiments of the invention lithium iron phosphate/carbon nano-tube nano composite material and preparation method above
It is discussed in detail.Principle and implementation of the present invention are described for specific embodiment used herein, and embodiment is said
It is bright to be merely used to help understand method and its core concept of the invention, the foregoing is merely presently preferred embodiments of the present invention and
, it is not intended to limit the invention, any modifications, equivalent replacements, and improvements done within the spirit and principles of the present invention
Deng should all be included in the protection scope of the present invention.
Claims (3)
1. a kind of preparation method of lithium iron phosphate/carbon nano-tube nano composite material of manufacture for anode material of lithium battery, should
Composite material is made of LiFePO4 core and carbon nanotube shell, and wherein lithium iron phosphate particles are olivine structural, aggregate particle size
It is 0.2 micron -10 microns；The carbon nanotube is wrapped in LiFePO4 surface, and the caliber of carbon nanotube is 2 nanometers -20 nanometers,
The internal diameter of carbon nanotube is 1 nanometer -10 nanometers, and the length of the carbon nanotube is 100 nanometers -1000 nanometers, it is characterised in that packet
Include following steps:
Step (1): the preparation of catalyst load LiFePO4 slurry
By lithium salts, microcosmic salt, molysite, Li:P:Fe=1:1:1 is weighed in molar ratio, while iron, nickel, molybdenum, a kind of in magnesium salts is added
Or multiple catalysts presoma, iron, nickel molar content be 2%-20%, the molar content of molybdenum is 2%-15%, mole of magnesium
Content is 25%-90%；Each component is stirred in a solvent, and adjusts pH value with alkali, it is anti-to be then added to hydro-thermal
It answers and is warming up to 300 DEG C of -800 DEG C of reaction 1h-24h in kettle, catalyst is made and loads LiFePO4 slurry；
Step (2): the preparation of lithium iron phosphate/carbon nano-tube nano composite material
Catalyst load LiFePO4 slurry is atomized above chemical vapor depsotition equipment (CVD) by spraying apparatus, atomization
Size droplet diameter afterwards is 1 micron -100 microns, and the drop after atomization enters high temperature reaction zone, and temperature is 600 DEG C -700 DEG C, with lazy
Property gas make carrier gas and be passed through one or more of methane, ethyl alcohol, acetylene, ethylene below CVD as carbon source, carbon source is passed through stream
Amount is 200SCCM-4000SCCM, and control catalyst load ferric lithium phosphate precursor slurry is in the high-temperature region CVD residence time 2h-
The reaction time of 8h, CVD process is controlled by high pressure draught in 20s-20min, and the lower section CVD obtains lithium iron phosphate/carbon nanotube and receives
Nano composite material.
2. a kind of lithium iron phosphate/carbon nano-tube nano composite material for anode material of lithium battery according to claim 1
Preparation method, it is characterised in that: the ferric lithium phosphate precursor salt is divided into lithium source, source of iron and phosphorus source three classes, wherein lithium source
For at least one of Li source compounds such as lithium hydroxide, lithium carbonate, lithium phosphate, lithium oxalate, lithium acetate；Source of iron is three oxidations two
At least one of iron, ferroso-ferric oxide, ferric phosphate, ferrous phosphate, ferrous oxalate, ferrous sulfate；Phosphorus source is phosphoric acid, di(2-ethylhexyl)phosphate
Hydrogen ammonium, diammonium hydrogen phosphate, ammonium phosphate, any one in ferric phosphate P source compound.
3. a kind of lithium iron phosphate/carbon nano-tube nano composite material for anode material of lithium battery according to claim 1
Preparation method, it is characterised in that: the solvent be at least one of dehydrated alcohol, methanol, acetone, propyl alcohol, with catalyst
The solid-to-liquid ratio for loading ferric lithium phosphate precursor is 6%-65%；The precursor material of the catalyst is divided into iron, nickel, molybdenum, magnesium four
Class, specially oxide, hydroxide, halide, sulfate, carbonate, nitrate, phosphate, acetate, oxalates, rouge
At least one of fat hydrochlorate, Metallocenic compound, metal carbonyl.
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| CN108232180A (en) * | 2017-12-19 | 2018-06-29 | 刘博文 | A kind of graphene/titanium dioxide/LiFePO4 aeroge cell positive material and preparation method thereof |
| CN109659531A (en) * | 2018-12-17 | 2019-04-19 | 中科廊坊过程工程研究院 | A kind of nickel cobalt lithium aluminate composite positive pole and its preparation method and application |
| AU2020264446A1 (en) | 2019-04-30 | 2021-11-18 | 6K Inc. | Mechanically alloyed powder feedstock |
| JP2023512391A (en) | 2019-11-18 | 2023-03-27 | シックスケー インコーポレイテッド | Unique feedstock and manufacturing method for spherical powders |
| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
| CN116034496A (en) | 2020-06-25 | 2023-04-28 | 6K有限公司 | Microcosmic composite alloy structure |
| CN111740115B (en) * | 2020-07-01 | 2021-07-16 | 中南大学 | Preparation method of lithium iron phosphate/carbon nanotube composite positive electrode material |
| CN111740113B (en) * | 2020-07-01 | 2021-07-16 | 中南大学 | Preparation method of lithium iron phosphate/carbon nanotube composite positive electrode material |
| CN111725516B (en) * | 2020-07-01 | 2023-05-05 | 中南大学 | LiFePO 4 Preparation method of CNTs composite positive electrode material |
| CN111740112B (en) * | 2020-07-01 | 2021-07-20 | 中南大学 | Preparation method of lithium iron phosphate/carbon nanotube composite positive electrode material |
| CN111732088B (en) * | 2020-07-01 | 2021-11-16 | 中南大学 | Lithium iron phosphate precursor/carbon nanotube composite material |
| CN111740104B (en) * | 2020-07-01 | 2021-07-16 | 中南大学 | Preparation method of lithium ferric manganese phosphate/carbon nanotube composite positive electrode material |
| KR20230073182A (en) | 2020-09-24 | 2023-05-25 | 6케이 인크. | Systems, devices and methods for initiating plasma |
| JP2023548325A (en) | 2020-10-30 | 2023-11-16 | シックスケー インコーポレイテッド | System and method for the synthesis of spheroidized metal powders |
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| CN102427130A (en) * | 2011-03-23 | 2012-04-25 | 上海中兴派能能源科技有限公司 | Lithium iron phosphate-carbon nanotube composite material, preparation method, and application thereof |
| CN105789620A (en) * | 2014-12-23 | 2016-07-20 | 深圳市比克电池有限公司 | Preparation method of lithium iron phosphate cathode material and lithium iron phosphate cathode material |
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