CN107881600A - A kind of preparation method and applications of carbon nano-fiber for negative electrode of lithium ion battery - Google Patents
A kind of preparation method and applications of carbon nano-fiber for negative electrode of lithium ion battery Download PDFInfo
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- CN107881600A CN107881600A CN201710838111.3A CN201710838111A CN107881600A CN 107881600 A CN107881600 A CN 107881600A CN 201710838111 A CN201710838111 A CN 201710838111A CN 107881600 A CN107881600 A CN 107881600A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to new energy materialses preparation and application technical field, a kind of preparation method and applications of carbon nano-fiber for negative electrode of lithium ion battery, wherein preparation method include procedure below：Rich nitrogen quinoline oligomer is prepared with quinoline, and in this, as rich nitrogen soft carbon presoma.Polyacrylonitrile prepares nanofiber as hard carbon presoma and spinning-aid agent by electrostatic spinning technique.Then it is warming up to 250 300 DEG C of pre-oxidation in air atmosphere, and be warming up to 600 1200 DEG C of carbonizations in a nitrogen atmosphere, obtain target material carbon nano-fiber.The carbon nano-fiber of the present invention has higher nitrogen content and good electric conductivity, has excellent high rate performance and cyclical stability as lithium ion battery negative material, preparation method provided by the invention is simple and easy, is easy to scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method and applications of the carbon nano-fiber for negative electrode of lithium ion battery, belong to new
Energy and material preparation and application technical field.
Background technology
Lithium ion battery as a new generation energy storage device, have energy density height, good cycling stability, it is environment-friendly with
And the advantage such as memory-less effect, it is widely used in the accumulation power supplies of the portable equipments such as mobile phone, Intelligent worn device and notebook.Pass
The commercial Li-ion battery negative pole graphite material of system, there is relatively low price and preferable cyclical stability, but graphite is electric
As negative electrode of lithium ion battery, its theoretical capacity is only 372mAh/g, and high rate performance is poor, can not increasingly meet electricity for pole
The use demand of sub- equipment.
Nitrogen-doped carbon material is increasingly becoming study hotspot in recent years, and doping nitrogen not only has stronger lithium ion energy of adsorption
Power, and position can reduce the diffusional resistance of lithium ion the defects of introducing, obtain higher quality specific capacity, more excellent times
Rate and cyclical stability.The logical normal manner of N doping hard carbon material graphitization journey is low, although this provides ideal for the storage of lithium ion
Avtive spot, but its electric conductivity is generally poor, is unfavorable for the quick transmission of electronics, and then causes its high rate performance poor.
In addition during first charge-discharge, the defects of material internal is excessive position can also cause bigger irreversible capacity loss and relatively low
Coulombic efficiency first.Comparatively speaking, soft carbon material specific surface area is relatively low, and defective bit is less, can effectively reduce irreversible appearance
The generation of amount, while also there is preferable multiplying power and cyclical stability, but its relatively low specific discharge capacity limits it and enters one
Step application.For patent 201510581382.6 using medium temperature coal pitch as soft carbon carbon source, polyacrylonitrile is hard carbon carbon source, prepares one kind
Asphalt-based nano carbon fiber, but nitrogen element content is extremely low in the medium temperature coal pitch of patent use, introduces medium temperature coal pitch and prepares
Carbon fiber substantially reduced compared with polyacrylonitrile-based carbon fibre nitrogen content, capacity declines notable, the matter under 100mA/g current densities
It is only 490.2mAh/g to measure specific capacity.
The content of the invention
In order to overcome the deficiencies in the prior art, the present invention seeks to for N doping hard carbon material multiplying power and circulation
Stability difference and itself and the significantly reduced phenomenon of the compound rear specific discharge capacity of soft carbon, there is provided one kind is used for negative electrode of lithium ion battery
Carbon nano-fiber preparation method and applications.The present invention is using rich nitrogen quinoline oligomer as soft carbon presoma, polyphosphazene polymer
Compound polyacrylonitrile is hard carbon presoma, and being prepared for one kind using electrostatic spinning technique and heat-treating methods is used for lithium-ion electric
The carbon nano-fiber of pond negative pole.The carbon nano-fiber that the present invention is prepared has higher nitrogen content and higher electrical conductivity,
Lithium ion battery negative material is used it as, has the advantages that specific capacity is high, good rate capability and cyclical stability are excellent concurrently.
In order to realize foregoing invention purpose, in the presence of solving the problems, such as prior art, the technical scheme of the invention taken
It is：A kind of preparation method of carbon nano-fiber for negative electrode of lithium ion battery, comprises the following steps：
Step 1, quinoline is added in round-bottomed flask first, nitrogen atmosphere protection is lower to add alchlor powder, heats 6-
12h, temperature control naturally cool to room temperature at 250-320 DEG C, obtain black solid particle, then using 1mol/L dilute salt
Acid and deionized water are washed successively, remove alchlor, then the solid particle after washing is dried in vacuo into 8-14h, temperature control
At 50-80 DEG C, rich nitrogen quinoline oligomer is obtained, the mass ratio of the alchlor and quinoline is 1.0：1.0-5.0；
After step 2, the rich nitrogen quinoline oligomer particles for obtaining step 1 are crushed to 5-10 microns, one part is taken to add
Into polar organic solvent, stirring 2-5h obtains the first stirring liquid, and then polyacrylonitrile is added in the first stirring liquid, heats
To 40-80 DEG C, stirring 2-5h obtains the second stirring liquid, and the mass ratio of the polyacrylonitrile and rich nitrogen quinoline oligomer is 1.0：
0.25-4.0, the polar organic solvent is in DMF, DMA or dimethyl sulfoxide (DMSO)
One kind, the polar organic solvent quality is 15-25g；
Step 3, the second stirring liquid obtained using step 2 prepare nanofiber as spinning solution using electrostatic spinning technique, quiet
Electrospun syringe needle internal diameter is 0.58-1.04mm, and metallic cylinder is collection device, and syringe needle to the distance between metallic cylinder is 10-
20cm, the voltage being applied on syringe needle are 14-20kV, and metallic cylinder rotating speed is controlled in 50-300r/min；
Step 4, the nanofiber for obtaining step 3 are put into tube furnace, and air is passed through with 0.5-1L/min gas velocity, with
0.5-3 DEG C/min heating rate rises to 250-300 DEG C, constant temperature pre-oxidation 1-5h, continues under nitrogen atmosphere protection with 1-5
DEG C/min heating rate rises to 600-1200 DEG C, constant temperature carbonization 1-5h, room temperature is naturally cooled to, obtains target material nano-sized carbon
Fiber.
Carbon nano-fiber prepared by methods described, the application on negative electrode of lithium ion battery.
Present invention has the advantages that：A kind of preparation method of carbon nano-fiber for negative electrode of lithium ion battery, including with
Lower step：(1) quinoline is added in round-bottomed flask first, the lower alchlor powder that adds of nitrogen atmosphere protection is heated, certainly
Room temperature so is cooled to, obtains black solid particle, is then washed successively using watery hydrochloric acid and deionized water, removes alchlor,
The solid particle after washing is dried in vacuo again, obtains rich nitrogen quinoline oligomer；(2) the rich nitrogen quinoline obtained step (1) is low
After glycolide particles are crushed to 5-10 microns, take one part to be added in polar organic solvent and be stirred, obtain the first stirring
Liquid, then polyacrylonitrile is added in the first stirring liquid and carries out heating stirring, obtains the second stirring liquid；(3) obtained with step (2)
The the second stirring liquid arrived is spinning solution, and nanofiber is prepared using electrostatic spinning technique；(4) Nanowire for obtaining step (3)
Dimension is put into tube furnace, is passed through the pre-oxidation of air constant temperature, and constant temperature is carbonized under nitrogen atmosphere protection, naturally cools to room temperature, obtains
To target material carbon nano-fiber.Compared with the prior art, process of the present invention is simple, convenient operation, it is easy to accomplish scale chemical industry
Industry produces.The a diameter of 200-300nm of carbon nano-fiber prepared by the present invention, nitrogen content are high, as lithium ion battery negative material,
With higher specific discharge capacity, and have good high rate performance and stable cycle performance concurrently.
Brief description of the drawings
Fig. 1 is carbon nano-fiber stereoscan photograph figure prepared by the embodiment of the present invention 1.
Fig. 2 is carbon nano-fiber X-ray diffractogram prepared by the embodiment of the present invention 1.
Fig. 3 is the lithium ion battery first charge-discharge curve map of the embodiment of the present invention 1.
Fig. 4 is the high rate performance figure of the lithium ion battery of the embodiment of the present invention 1 discharge and recharge under different current densities.
Fig. 5 is the cycle performance figure of the lithium ion battery of the embodiment of the present invention 1.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
Weigh 150g quinoline to add in 500mL round-bottomed flasks, nitrogen atmosphere protection is lower to add 50g alchlor powder, adds
Hot 10h, temperature control naturally cool to room temperature at 300 DEG C, are then washed successively using 1mol/L watery hydrochloric acid and deionized water
Wash, remove alchlor, then the solid particle after washing is dried in vacuo 12h, it is low to obtain rich nitrogen quinoline at 60 DEG C for temperature control
Polymers；After rich nitrogen quinoline oligomer particles are crushed into 8 microns again, its powder 3g is taken to be added to 18g DMFs
In, stirring 4h obtains the first stirring liquid, and then 3g polyacrylonitrile is added in the first stirring liquid, is heated to 60 DEG C, stirs 4h
Obtain the second stirring liquid；Using the second obtained stirring liquid as spinning solution, nanofiber, Static Spinning are prepared using electrostatic spinning technique
Silk syringe needle internal diameter is 0.84mm, and metallic cylinder is collection device, and syringe needle to the distance between metallic cylinder is 15cm, is applied to syringe needle
On voltage be 18kV, metallic cylinder rotating speed is controlled in 200r/min；Obtained nanofiber is put into tube furnace again, with
0.5L/min gas velocity is passed through air, rises to 280 DEG C with 1 DEG C/min heating rate, constant temperature pre-oxidation 2h, is protected in nitrogen atmosphere
Lower continuation rises to 700 DEG C with 3 DEG C/min heating rate, constant temperature carbonization 2h, naturally cools to room temperature, obtains target material nanometer
Carbon fiber.
Using the carbon nano-fiber of preparation as integral electrodes, 1mol/L LiPF6Binary solvent mixtures press EC/DEC
=1:The electrolyte of 1 volume ratio mixing, polypropylene film is barrier film, and CR2016 is assembled into the glove box full of argon gas
Button cell.Charge-discharge test is carried out on the Land CT2001A type battery test systems of Wuhan, charging/discharging voltage scope
For 0.01-3V.
Fig. 1 is carbon nano-fiber stereoscan photograph figure prepared by the present invention, it can be seen that the fiber shape of preparation is kept
Completely, in 200-300nm, fiber is interweaved in three-dimensional network shape diameter, and passage is provided for the quick transmission of electronics.Fig. 2
It is carbon nano-fiber X-ray diffractogram prepared by the present invention, the carbon nano-fiber nitrogen element content of preparation is 12.1wt%.Fig. 3
It is that carbon nano-fiber prepared by the present invention is used as charge and discharge first of the lithium ion battery negative material under 0.1A/g current density
The specific discharge capacity of electric curve, wherein initial charge is 764.9mAh/g.Fig. 4 is that carbon nano-fiber prepared by the present invention is used as lithium
High rate performance of the ion battery cathode material under different current densities, the reversible discharge capacity under 0.1A/g current densities are high
Up to 748.3mAh/g, the reversible discharge capacity under 10A/g current densities is still up to 340.2mAh/g, capability retention
45.5%, electrical conductivity 0.47S/m.Fig. 5 is that carbon nano-fiber prepared by the present invention is used as lithium ion battery negative material in 2A/
Cycle performance under g current densities, circulation conservation rate are 91.7%.
Embodiment 2
Weigh 50g quinoline to add in 500mL round-bottomed flasks, nitrogen atmosphere protection is lower to add 50g alchlor powder, heating
6h, temperature control naturally cool to room temperature at 250 DEG C, are then washed, removed successively using 1mol/L watery hydrochloric acid and deionized water
Alchlor is removed, then the solid particle after washing is dried in vacuo 8h, temperature control obtains rich nitrogen quinoline oligomer at 50 DEG C；
After rich nitrogen quinoline oligomer particles are crushed into 5 microns again, take its powder 1g to be added in 15g DMAs, stir
Mix 2h and obtain the first stirring liquid, then 4g polyacrylonitrile is added in the first stirring liquid, be heated to 40 DEG C, stirring 2h obtains the
Two stirring liquid；Using the second obtained stirring liquid as spinning solution, nanofiber, electrostatic spinning syringe needle are prepared using electrostatic spinning technique
Internal diameter is 0.58mm, and metallic cylinder is collection device, and syringe needle to the distance between metallic cylinder is 10cm, the electricity being applied on syringe needle
Press and controlled for 14kV, metallic cylinder rotating speed in 50r/min；Obtained nanofiber is put into tube furnace again, with 0.5L/min
Gas velocity is passed through air, rises to 250 DEG C with 0.5 DEG C/min heating rate, constant temperature pre-oxidation 1h, continues under nitrogen atmosphere protection
600 DEG C are risen to 1 DEG C/min heating rate, constant temperature carbonization 1h, room temperature is naturally cooled to, obtains target material Nano carbon fibers
Dimension.
Using the carbon nano-fiber of preparation as integral electrodes, 1mol/L LiPF6Binary solvent mixtures press EC/DEC
=1:The electrolyte of 1 volume ratio mixing, polypropylene film is barrier film, and CR2016 is assembled into the glove box full of argon gas
Button cell, charge-discharge test are carried out on the Land CT2001A type battery test systems of Wuhan, charging/discharging voltage scope
For 0.01-3V.
The nitrogen content for measuring the carbon nano-fiber negative material of preparation is 14.8wt%, under 0.1A/g current densities can
Inverse put capacitance reaches 608.6mAh/g, and the reversible discharge capacity under 10A/g current densities is 240.7mAh/g, and capability retention is
Circulation conservation rate under 39.5%, 2A/g current density is 87.5%.
Embodiment 3
Weigh 250g quinoline to add in 500mL round-bottomed flasks, nitrogen atmosphere protection is lower to add 50g alchlor powder, adds
Hot 12h, temperature control naturally cool to room temperature at 300 DEG C, are then washed successively using 1mol/L watery hydrochloric acid and deionized water
Wash, remove alchlor, then the solid particle after washing is dried in vacuo 14h, it is low to obtain rich nitrogen quinoline at 80 DEG C for temperature control
Polymers；After rich nitrogen quinoline oligomer particles are crushed into 10 microns again, take its powder 8g to be added in 25g dimethyl sulfoxide (DMSO)s, stir
Mix 5h and obtain the first stirring liquid, then 2g polyacrylonitrile is added in the first stirring liquid, be heated to 80 DEG C, stirring 5h obtains the
Two stirring liquid；Using the second obtained stirring liquid as spinning solution, nanofiber, electrostatic spinning syringe needle are prepared using electrostatic spinning technique
Internal diameter is 1.04mm, and metallic cylinder is collection device, and syringe needle to the distance between metallic cylinder is 20cm, the electricity being applied on syringe needle
Press and controlled for 20kV, metallic cylinder rotating speed in 300r/min；Obtained nanofiber is put into tube furnace again, with 1L/min gas
Speed is passed through air, rises to 300 DEG C with 3 DEG C/min heating rate, constant temperature pre-oxidation 5h, continues under nitrogen atmosphere protection with 5
DEG C/min heating rate rises to 1200 DEG C, constant temperature carbonization 5h, room temperature is naturally cooled to, obtains target material carbon nano-fiber.
Using the carbon nano-fiber of preparation as integral electrodes, 1mol/L LiPF6Binary solvent mixtures press EC/DEC
=1:The electrolyte of 1 volume ratio mixing, polypropylene film is barrier film, and CR2016 is assembled into the glove box full of argon gas
Button cell.Charge-discharge test is carried out on the Land CT2001A type battery test systems of Wuhan, charging/discharging voltage scope
For 0.01-3V.
It is 10.4wt% to measure and prepare the nitrogen content of carbon nano-fiber negative material, reversible under 0.1A/g current densities
Discharge capacity is 627.1mAh/g, and the reversible discharge capacity under 10A/g current densities is 254.6mAh/g, and capability retention is
Circulation conservation rate under 40.6%, 2A/g current density is 86.3%.
Comparative example 1
Weigh 3g polyacrylonitrile powders to be added in 18g DMFs, be heated to 60 DEG C, stir 4h, with
The stirring liquid arrived is spinning solution, prepares polyacrylonitrile nanofiber using electrostatic spinning technique, electrostatic spinning syringe needle internal diameter is
0.84mm, metallic cylinder are collection device, and the distance of syringe needle to metallic cylinder is 15cm, and the voltage being applied on syringe needle is
20kV；Obtained polyacrylonitrile nanofiber is put into tube furnace again, air is passed through with 0.5L/min gas velocity, with 1 DEG C/min
Heating rate rise to 280 DEG C, constant temperature pre-oxidation 2h, continue to rise to 3 DEG C/min heating rate under nitrogen atmosphere protection
700 DEG C, constant temperature carbonization 2h, room temperature is naturally cooled to, obtains polyacrylonitrile base nano carbon fibre.
Using the polyacrylonitrile base nano carbon fibre of preparation as integral electrodes, 1mol/L LiPF6Bi-component mixing it is molten
EC/DEC=1 is pressed in agent:The electrolyte of 1 volume ratio mixing, polypropylene film is barrier film, the group in the glove box full of argon gas
Dress up CR2016 button cells.Charge-discharge test is carried out on the Land CT2001A type battery test systems of Wuhan, charge and discharge
Piezoelectric voltage scope is 0.01-3V.
The nitrogen content for measuring the polyacrylonitrile base nano carbon fibre negative material of preparation is 18.2wt%, in 0.1A/g electric currents
Reversible discharge capacity under density reaches 639.7mAh/g, and the reversible discharge capacity under 10A/g current densities is only 119.7mAh/g,
Capability retention is only 18.7%, and high rate performance is poor, the circulation conservation rate under electrical conductivity 0.098S/m, 2A/g current density
Only 61.5%.
Comparative example 2
After medium temperature coal pitch is crushed into 8 microns, 3g medium temperature coal pitch powder is taken to be added to 18g N, N- dimethyl formyls
In amine, stirring 4h obtains the first stirring liquid, and 3g polyacrylonitrile is added in the first stirring liquid, is heated to 60 DEG C, stirs 4h, obtains
To the second stirring liquid；Using the second obtained stirring liquid as spinning solution, nanofiber, electrostatic spinning are prepared using electrostatic spinning technique
Syringe needle internal diameter is 0.84mm, and metallic cylinder is collection device, and the distance of syringe needle to metallic cylinder is 15cm, is applied on syringe needle
Voltage is 20kV；
Obtained nanofiber is put into tube furnace again, air is passed through with 0.5L/min gas velocity, with 1 DEG C/min heating
Speed rises to 280 DEG C, constant temperature pre-oxidation 2h, continues to rise to 700 DEG C with 3 DEG C/min heating rate under nitrogen atmosphere protection,
Constant temperature carbonization 2h, naturally cools to room temperature, obtains carbon nano-fiber.
Using the carbon nano-fiber of preparation as integral electrodes, 1mol/L LiPF6Binary solvent mixtures press EC/DEC
=1:The electrolyte of 1 volume ratio mixing, polypropylene film is barrier film, and CR2016 is assembled into the glove box full of argon gas
Button cell.Charge-discharge test is carried out on the Land CT2001A type battery test systems of Wuhan, charging/discharging voltage scope
For 0.01-3V.
The nitrogen content for measuring the carbon nano-fiber of preparation is 7.1wt%, and the reversible discharge under 0.1A/g current densities holds
It is only 482.5mAh/g to measure, and the reversible discharge capacity under 10A/g current densities is only 150.7mAh/g, and capability retention is
31.2%.Circulation conservation rate under 2A/g current densities is 74.5%.
Claims (2)
1. the preparation method of a kind of carbon nano-fiber for negative electrode of lithium ion battery, it is characterised in that comprise the following steps：
Step 1, quinoline being added in round-bottomed flask first, nitrogen atmosphere protection is lower to add alchlor powder, heats 6-12h,
Temperature control naturally cools to room temperature at 250-320 DEG C, obtains black solid particle, then using 1mol/L watery hydrochloric acid and
Deionized water is washed successively, removes alchlor, then the solid particle after washing is dried in vacuo into 8-14h, and temperature control is in 50-
80 DEG C, rich nitrogen quinoline oligomer is obtained, the mass ratio of the alchlor and quinoline is 1.0：1.0-5.0；
After step 2, the rich nitrogen quinoline oligomer particles for obtaining step 1 are crushed to 5-10 microns, one part is taken to be added to pole
Property organic solvent in, stirring 2-5h obtain the first stirring liquid, then polyacrylonitrile is added in the first stirring liquid, is heated to
40-80 DEG C, stirring 2-5h obtains the second stirring liquid, and the mass ratio of the polyacrylonitrile and rich nitrogen quinoline oligomer is 1.0：
0.25-4.0, the polar organic solvent is in DMF, DMA or dimethyl sulfoxide (DMSO)
One kind, the polar organic solvent quality is 15-25g；
Step 3, the second stirring liquid obtained using step 2 prepare nanofiber, Static Spinning as spinning solution using electrostatic spinning technique
Silk syringe needle internal diameter is 0.58-1.04mm, and metallic cylinder is collection device, and syringe needle to the distance between metallic cylinder is 10-20cm, is applied
The voltage being added on syringe needle is 14-20kV, and metallic cylinder rotating speed is controlled in 50-300r/min；
Step 4, the nanofiber for obtaining step 3 are put into tube furnace, air are passed through with 0.5-1L/min gas velocity, with 0.5-3
DEG C/min heating rate rises to 250-300 DEG C, constant temperature pre-oxidation 1-5h, continue under nitrogen atmosphere protection with 1-5 DEG C/min
Heating rate rise to 600-1200 DEG C, constant temperature carbonization 1-5h, naturally cool to room temperature, obtain target material carbon nano-fiber.
2. the carbon nano-fiber that according to claim 1 prepared by method, the application on negative electrode of lithium ion battery.
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Cited By (3)
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|---|---|---|---|---|
| CN112086629A (en) * | 2020-09-08 | 2020-12-15 | 合肥国轩高科动力能源有限公司 | Si @ C/ZnNb2O6Preparation method and application of negative electrode composite material |
| CN113224292A (en) * | 2021-02-02 | 2021-08-06 | 江西理工大学 | High-performance lithium ion battery polyacrylonitrile carbon fiber negative electrode material and preparation method thereof |
| CN114267829A (en) * | 2021-12-08 | 2022-04-01 | 新疆大学 | Preparation method of coal-based porous carbon fiber negative electrode material of lithium/sodium ion battery |
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