CN105336921B - A kind of preparation method and applications of carbon nano-fiber - Google Patents
A kind of preparation method and applications of carbon nano-fiber Download PDFInfo
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- CN105336921B CN105336921B CN201510623535.9A CN201510623535A CN105336921B CN 105336921 B CN105336921 B CN 105336921B CN 201510623535 A CN201510623535 A CN 201510623535A CN 105336921 B CN105336921 B CN 105336921B
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
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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 preparation method and the application in lithium ion battery negative material that the present invention discloses a kind of graphited carbon nano-fiber product of the concrete dynamic modulus as lithium ion battery negative material, the present invention is with N, N dimethylformamides are solvent, using polyacrylonitrile as high molecular polymer, electrostatic spinning solution has been prepared.The pattern of Electrospun nano-fibers is strengthened with pre-oxidation, it converts PAN to graphited carbon by being calcined in argon gas atmosphere high temperature, the fiber of calcining is continued into calcining in air and is prepared for the graphited carbon nano-fiber of concrete dynamic modulus, and as lithium ion battery negative material, the assembling and performance test of button cell are carried out, test shows that the graphited carbon nano-fiber of concrete dynamic modulus has extraordinary chemical property as lithium ion battery negative material.
Description
Technical field
The invention belongs to the production technology of material and application fields, and in particular to a kind of to be used as lithium ion battery negative material
Carbon nano-fiber technology of preparing.
Background technology
The positive electrode of commercial lithium ion battery mainly has LiCoO at present2、LiMn2O4、LiFePO4And LiNiO2Deng, by
There is reasonable price in graphite, the advantages such as chemical potential is low, for main commercialized negative material currently on the market.But stone
The theoretical capacity of ink is relatively low, only 372 m Ah g-1, and its theoretical capacity is had reached at present.Currently, by carbonaceous material into
Row is modified for lithium ion battery material, it has also become the hot spot of research.
Invention content
It is an object of the invention to propose a kind of easy to operate, repeatable strong carbon can be used for negative electrode of lithium ion battery
The preparation method of nanofiber article.
The present invention includes following sequential steps：
1）Polyacrylonitrile (PAN) and N,N-dimethylformamide (DMF) are mixed with electrostatic spinning liquid；
2）Electrostatic spinning liquid is subjected to electrostatic spinning, obtains Electrospun nano-fibers；
3）Electrospun nano-fibers are weaved, Electrospun nano-fibers cloth is obtained；
4）Electrospun nano-fibers cloth is pre-oxidized with the pattern of anchoring fiber；
5）By the Electrospun nano-fibers cloth high-temperature calcination in an inert atmosphere of pre-oxidation, it converts polyacrylonitrile to stone
The C of inkization；
6）Graphited Electrospun nano-fibers cloth after high-temperature calcination is continued to calcine in air atmosphere, is obtained
Graphited carbon nano-fiber product with a large amount of holes.
The present invention is prepared for nanofiber by method of electrostatic spinning, and graphited carbon has been made by further high-temperature calcination
Fiber is calcined finally by air atmosphere so that the inside of fiber produces more hole, this is conducive to lithium ion
The raising of transmission and its chemical property.Graphited carbon nano-fiber with a large amount of holes can be born as lithium ion battery
Pole material, this research have certain promotion to make to promoting or improving carbonaceous material as the performance of lithium ion battery negative material
With.
Further, polyacrylonitrile of the present invention and the mixing quality of n,N-Dimethylformamide ratio are 6~12: 100,
The viscosity of the electrostatic spinning liquid prepared with the proportioning is suitble to electrostatic spinning, and the voltage of electrostatic spinning and reception distance is coordinated to prepare
Go out the uniform Electrospun nano-fibers of pattern.
The voltage of electrostatic spinning of the present invention be 5~20 kV, receive distance be 5~20cm, electrostatic spinning syringe needle it is interior
Diameter is 0.2~0.5 mm, and the fltting speed of electrostatic spinning liquid is 0.2~1.5mL/h, and aluminium foil is attached to metal baffle or roller
Upper reception Electrospun nano-fibers, drum rotation speed are 10~50 r/min.The fiber continuity of acquirement is good, and fineness is stable, equal
It is even.
Pre-oxidation of the present invention is carried out in tube furnace, pre-prepared precursor is placed in the middle part of boiler tube, with 1~6mL/
The flow of min is passed through air, and with the heating rate of 1~2 DEG C/min, 240~260 DEG C are risen to from room temperature, and maintain 60~
180min.Pre-oxidation is the pattern for anchoring fiber.It is to ensure in preoxidation process just to be passed through a small amount of dry air
Normal air exchange.
Step 5 of the present invention）Described in high-temperature calcination be to be carried out in tube furnace, by the Electrospun nano-fibers of pre-oxidation
It is arranged in quartz boat, is subsequently placed in the middle part of boiler tube, and be passed through argon gas, with the heating rate of 3~7 DEG C/min, is risen to from room temperature
900~1200 DEG C, and maintain 60~150min.Calcining can convert PAN to height in an inert atmosphere under this hot conditions
The graphited carbon of electric conductivity.
Step 6 of the present invention）Described in calcining be to be carried out in tube furnace, Electrospun nano-fibers are arranged in quartz boat
In be subsequently placed in the middle part of boiler tube, the opening of tube furnace is threaded to maximum, or air is passed through with the flow of 0~2mL/min, with 3~6
DEG C/heating rate of min, 350~450 DEG C are risen to from room temperature, and maintain 120~1500min.This method can will be in fiber
Part carbon removes, and has prepared more lacunose graphited carbon nano-fiber.The air being passed through will ensure the oxidation of carbon material
Required oxygen, porous performance are beneficial to the diffusion of lithium ion, therefore are conducive to obtain higher circulation volume and preferably
Cyclical stability.The pattern of nanofiber of the present invention is uniform, according to the difference of calcination temperature and calcination time, fiber
A diameter of 100~400 nm.
The present invention another object is that propose the above method prepare the graphited carbon nano-fiber product application of concrete dynamic modulus in
In lithium ion battery.
Will be dry after the graphited carbon nano-fiber product cut-parts of concrete dynamic modulus, then it is used as lithium ion battery negative material group
In button cell.
Since the characteristics such as conductive good, the raw material rich reserves of carbon material are widely ground what electrochemical field obtained
Study carefully and apply, wherein graphite is the negative material of commercialized lithium ion battery.This research is to the carbon material with higher performance
Certain impetus is played in commercialization as lithium ion battery negative material.
The assemble method of lithium ion battery electrode material of the present invention is one of following three kinds：
1, using the solution of the 1-Methyl-2-Pyrrolidone of the Kynoar of 0.01~0.02 g/mL as binder, by carbon
Nanofiber article is adhered on copper foil, is then dried in vacuum drying chamber, and lithium ion cell electrode is made；The lithium ion
The mass ratio of Kynoar and carbon nano-fiber product is 2~15: 100 in battery electrode.
2, the ratio for being 0.5~1: 1 in the mixing quality of sodium carboxymethylcellulose and butadiene-styrene rubber ratio, by mass percent
Aqueous solution for 0.5~2% sodium carboxymethylcellulose is mixed to form binder with butadiene-styrene rubber, and carbon nano-fiber product is glued
It invests on copper foil, is then dried in vacuum drying chamber, lithium ion cell electrode is made；Carboxymethyl in the lithium ion cell electrode
The mass ratio of the gross mass and fiber cloth of sodium cellulosate and butadiene-styrene rubber is 1~15: 100.
3, the assembling of battery is directly carried out after drying carbon nano-fiber product.
Assembling through button cell, test show：By pre-oxidation and air of the graphited nanofiber at 400 DEG C
3 h are calcined in atmosphere, the graphited carbon nano-fiber of concrete dynamic modulus of 8 h and 18 h are in 0.5 A g-1Current density under charge and discharge
Its discharge capacity is respectively maintained at 288.7,366.8 and 452.0 mA h g after 100 circle of cycle-1, shown higher charge and discharge
The cyclical stability that capacitance is become reconciled.
Description of the drawings
Fig. 1 is that the electrostatic spinning object prepared in specific implementation mode one passes through the scanning of the nanofiber prepared after pre-oxidation
Electron microscope.
Fig. 2 is the partial enlarged view of Fig. 1.
Fig. 3 is that the electrostatic spinning object for preparing passes through the Nanowire that is prepared after pre-oxidation and graphitization in specific implementation mode one
The scanning electron microscope (SEM) photograph of dimension.
Fig. 4 is the partial enlarged view of Fig. 3.
Fig. 5 is to continue in air after the electrostatic spinning object for preparing is by pre-oxidation and graphitization in specific implementation mode one
The scanning electron microscope (SEM) photograph of the nanofiber of 3 h preparations is calcined in atmosphere.
Fig. 6 is the partial enlarged view of Fig. 5.
Fig. 7 is to continue in air after the electrostatic spinning object for preparing is by pre-oxidation and graphitization in specific implementation mode one
The scanning electron microscope (SEM) photograph of the nanofiber of 8 h preparations is calcined in atmosphere.
Fig. 8 is the partial enlarged view of Fig. 7, typical a diameter of 252 nm.
Fig. 9 is to continue in air after the electrostatic spinning object for preparing is by pre-oxidation and graphitization in specific implementation mode one
The scanning electron microscope (SEM) photograph of the nanofiber of 18 h preparations is calcined in atmosphere.
Figure 10 is the partial enlarged view of Fig. 9.
Figure 11 be in specific implementation mode one the electrostatic spinning object for preparing by after pre-oxidation and graphitization and continuing in sky
Specific surface area (BET) test chart of the nanometer line fiber of 3 h preparations is calcined in gas atmosphere.
Figure 12 is that the electrostatic spinning object for preparing passes through the nanometer that is prepared after pre-oxidation and graphitization in specific implementation mode one
The transmission electron microscope picture of fiber.
Figure 13 is the partial enlarged view of Figure 12.
Figure 14 is to continue in air after the electrostatic spinning object for preparing is by pre-oxidation and graphitization in specific implementation mode one
The scanning electron microscope (SEM) photograph of the nanofiber of 18 h preparations is calcined in atmosphere.
Figure 15 is the partial enlarged view of Figure 14.
Figure 16 is to continue in air after the electrostatic spinning object for preparing is by pre-oxidation and graphitization in specific implementation mode one
Calcined in atmosphere 3 h, 8 h and 18 h preparation nanofiber as lithium ion battery electrode material in 0.5 A g-1Electric current it is close
Charge-discharge performance curve under degree.
Specific implementation mode
One, the preparation method of the graphited carbon nano-fiber product of concrete dynamic modulus：
1, the preparation of spinning solution：1.0 g polyacrylonitrile (PAN) and 9.0 g N, N- diformazans are added in 25 mL conical flasks
Base formamide (DMF), 12~36 h of room temperature magnetic agitation, prepares uniform electrostatic spinning liquid.
2, electrostatic spinning：The syringe that spinning solution is poured into 10 mL capacity, is put into electrostatic spinning apparatus, aluminium foil is adhered to
In metal
Electrospun nano-fibers are collected on baffle, voltage is set as 13~17 KV, and it is 10~18 cm to receive distance, into
Row electrostatic spinning obtains Electrospun nano-fibers.
3, it weaves：Machine on Electrospun nano-fibers is weaved, Electrospun nano-fibers cloth is obtained.
4, it pre-oxidizes：It after Electrospun nano-fibers cloth is cut into fritter, is put into quartz boat, is placed in tube furnace,
It is passed through the dry air of small flow, flow velocity is 1~6 mL/min, and 240~260 are warming up to the heating rate of 1~2 DEG C/min
DEG C, and maintain 60~180 min.
5, the preparation of graphited carbon nano-fiber：Electrospun fibers cloth after pre-oxidation is put into tube furnace, is led to
Enter the high-purity argon gas of small flow, flow velocity is that 1~6 mL/min rises to 1000 with the heating rate of 3~7 DEG C/min from room temperature
DEG C and maintain 60~150 min, convert PAN to graphited carbon.
6, the preparation of the graphited carbon nano-fiber product of concrete dynamic modulus：Graphited electrospun fibers cloth is put into quartz
In boat and it is positioned over position among tube furnace, the opening of tube furnace is threaded to maximum or is passed through with the rate of 0~2 mL/min
Certain air is risen to 400 DEG C from room temperature, and maintain 120~1500 min, is prepared with the heating rate of 3~6 DEG C/min
The graphited carbon nano-fiber product of concrete dynamic modulus.
Two, the assembling of lithium ion battery is carried out using the material of preparation as lithium ion battery negative material product：
The graphited carbon nano-fiber product of concrete dynamic modulus is cut to battery pole as lithium ion battery negative material product
The size of piece, at 60~120 DEG C（It is preferred that 80 DEG C）Vacuum drying chamber in dry 8~16 h, to remove a small amount of water in fiber
Point.
Due to the difference of fibre plate thickness in the present invention, the quality of the fibre plate after cutting is that 1~8 mg is differed.After weighing
Directly as lithium ion battery anode active material, the assembling of 2032 model button cells is carried out.
The assembling that battery is carried out by following 3 kinds of modes, can assemble to obtain lithium ion battery negative material.
1, it is viscous with the solution of the 1-Methyl-2-Pyrrolidone (NMP) of the Kynoar (PVDF) of 0.01 g/mL
Agent is tied, fibre is adhered on copper foil, is then dried in vacuum drying chamber, lithium ion cell electrode is made.It is manufactured
Kynoar (PVDF) and the mass ratio of fiber cloth are 2~15: 100 in lithium ion cell electrode.
2, the ratio for being 0.5~1: 1 in mixing quality ratio, by the carboxymethyl cellulose for being 0.5~2% containing mass percent
The aqueous solution of plain sodium (CMC) is mixed to form binder with butadiene-styrene rubber (SBR), fibre is adhered on copper foil, so
It is dried in vacuum drying chamber afterwards, lithium ion cell electrode is made.Carboxymethyl cellulose in the manufactured lithium ion cell electrode
The mass ratio of the gross mass and fiber cloth of plain sodium (CMC) and butadiene-styrene rubber (SBR) is 1~15: 100.
3, the fibre after drying is directly subjected to battery under the conditions of not adding binder and not having to the mode of copper foil
Assembling.
After the fibre grinding after drying, spinning fibre mass fraction 0 is added according to the proportioning of above-mentioned binder
As conductive additive, the electrode material by stirring, coating and drying continues to be placed in 120 DEG C of baking oven~15% carbon black
Dry 6~24 h, are then transferred in glove box rapidly, carry out the assembling of button cell.
It is to electrode with lithium piece, the calculating of the size of charging and discharging currents is with the graphited carbon nano-fiber product of concrete dynamic modulus
Quality is foundation, and 0.01~3.0 V of voltage range passes through 0.5 A g-1Current density in air atmosphere it is different calcine when
Between the graphited carbon nano-fiber product charge and discharge cycles 100 of concrete dynamic modulus enclose to investigate the stability of its performance and cycle.
Three, performance characterization：
Fig. 1 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidized under the conditions of 250 DEG C 2 h preparation nanofiber scanning electron microscope (SEM) photograph.Fig. 2 is the office of Fig. 1
Portion's enlarged drawing, 391 nm of the typical diameter of nanofiber.
Fig. 3 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C after, calcined in 1000 DEG C of Ar atmosphere 2 h preparation fiber
Scanning electron microscope (SEM) photograph.Fig. 4 is its partial enlarged view.The diameter of wherein fiber is significantly less than the fiber pre-oxidized by 250 DEG C
Diameter, representational a diameter of 340 nm.
Fig. 5 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C after, calcine 2 h in 1000 DEG C of Ar atmosphere, continue 400
DEG C air atmosphere in calcine 3 h preparation nanofiber scanning electron microscope (SEM) photograph.Fig. 6 is the partial enlarged view of Fig. 5.
Fig. 7 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C after, calcine 2 h in 1000 DEG C of Ar atmosphere, continue 400
DEG C air atmosphere in calcine 8 h preparation nanofiber scanning electron microscope (SEM) photograph.Fig. 8 is the partial enlarged view of Fig. 7, typical straight
Diameter is 252 nm.
Fig. 9 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C after, calcine 2 h in 1000 DEG C of Ar atmosphere, continue 400
DEG C air atmosphere in calcine 18 h preparation nanofiber scanning electron microscope (SEM) photograph.Figure 10 is the partial enlarged view of Fig. 9, has generation
A diameter of 217 nm of table, this shows in 400 DEG C of air as prolonged calcining, the diameter of fiber have certain journey
The reduction of degree.
Figure 11 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C after, calcined in 1000 DEG C of Ar atmosphere 2 h preparation nanometer
Fiber and the specific surface area test chart for continuing to calcine the nanofiber of 3 h preparations in 400 DEG C of air atmosphere.By in figure
As can be seen that after graphited carbon nano-fiber in 400 DEG C of air atmosphere by calcining 3 h, specific surface area have compared with
Big promotion is respectively 40.6 and 542.6 m by calculating its value2/g。
Figure 12 is to be made under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
After standby electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C, receiving for 2 h preparations is calcined in 1000 DEG C of Ar atmosphere
The transmission electron microscope picture of rice fiber.Figure 13 is the partial enlarged view of Figure 12, and color is deeper, shows that the porosity in fiber is smaller.
Figure 14 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C after, calcine 2 h in 1000 DEG C of Ar atmosphere, continue 400
DEG C air atmosphere in calcine 18 h preparation nanofiber transmission electron microscope picture.Figure 15 is the partial enlarged view of Figure 14, face
Color is shallower, shows that the porosity in fiber is larger.
Figure 16 is to be prepared under 15 KV voltages using 1.0 g PAN and 9.0 g DMF as spinning solution in specific implementation mode one
Electrospun fibers pre-oxidize 2 h under the conditions of 250 DEG C after, calcine 2 h in 1000 DEG C of Ar atmosphere, continue 400
DEG C air atmosphere in calcine 3h, 8h and 18 h preparation nanofiber directly as electrode material in 0.5 A g-1Electric current it is close
Charge-discharge performance figure under degree, after 100 circle cycles, discharge capacity is respectively：288.7,366.8 and 452.0 mA
H/g shows higher capacity and preferable cyclical stability.This shows porosity to the nanofiber of preparation as lithium
The performance of ion electrode materials has very important effect.
Claims (7)
1. a kind of preparation method of carbon nano-fiber product, it is characterised in that including following sequential steps：
1）Polyacrylonitrile and N,N-dimethylformamide are mixed with electrostatic spinning liquid；
2）Electrostatic spinning liquid is subjected to electrostatic spinning, obtains Electrospun nano-fibers；
3）Electrospun nano-fibers are weaved, Electrospun nano-fibers cloth is obtained；
4）Electrospun nano-fibers cloth is pre-oxidized with the pattern of anchoring fiber；The pre-oxidation is carried out in tube furnace,
It after Electrospun nano-fibers cloth is cut into fritter, is put into quartz boat, is placed in tube furnace, with the flow of 1~6mL/min
It is passed through air, with the heating rate of 1~2 DEG C/min, rises to 240~260 DEG C from room temperature, and maintain 60~180min；
5）By the Electrospun nano-fibers cloth high-temperature calcination in an inert atmosphere of pre-oxidation, it converts polyacrylonitrile to graphitization
C；
6）Graphited Electrospun nano-fibers cloth after high-temperature calcination is continued to calcine in air atmosphere, acquirement has
The graphited carbon nano-fiber product of a large amount of holes；Step 6）Described in calcining be to be carried out in tube furnace, by electrostatic spinning
Nanofiber, which is arranged in quartz boat, to be subsequently placed in the middle part of boiler tube, air is passed through with the flow of 2mL/min, with 3~6 DEG C/min's
Heating rate rises to 350~450 DEG C from room temperature, and maintains 120~1500min.
2. preparation method according to claim 1, it is characterised in that the polyacrylonitrile and n,N-Dimethylformamide it is mixed
It is 6~12: 100 to close mass ratio.
3. preparation method according to claim 1, it is characterised in that the voltage of the electrostatic spinning be 5~20 kV, receive away from
It is 0.2~0.5 mm from the internal diameter for 5~20cm, electrostatic spinning syringe needle, the fltting speed of electrostatic spinning liquid is 0.2~1.5mL/
Aluminium foil is attached in metal baffle or roller and receives Electrospun nano-fibers by h, and drum rotation speed is 10~50 r/min.
4. preparation method according to claim 1, it is characterised in that step 5）Described in high-temperature calcination be in tube furnace into
Row, the Electrospun nano-fibers of pre-oxidation are arranged in quartz boat, are subsequently placed in the middle part of boiler tube, and be passed through argon gas, with 3~
The heating rate of 7 DEG C/min rises to 900~1200 DEG C from room temperature, and maintains 60~150min.
5. the application of carbon nano-fiber product prepared by method as described in claim 1 in lithium ion battery, by carbon Nanowire
It is dry after fiber products cut-parts, then it is assembled in button cell as lithium ion battery negative material；It is characterized in that with 0.01
The solution of the 1-Methyl-2-Pyrrolidone of the Kynoar of~0.02 g/mL is binder, and carbon nano-fiber product is adhered to
It on copper foil, is then dried in vacuum drying chamber, lithium ion cell electrode is made；Gather inclined fluorine in the lithium ion cell electrode
The mass ratio of ethylene and carbon nano-fiber product is 2~15: 100.
6. the application of carbon nano-fiber product prepared by method as described in claim 1 in lithium ion battery, by carbon Nanowire
It is dry after fiber products cut-parts, then it is assembled in button cell as lithium ion battery negative material；It is characterized in that pressing carboxylic first
The ratio that the mixing quality of base sodium cellulosate and butadiene-styrene rubber ratio is 0.5~1: 1, the carboxylic first for being 0.5~2% by mass percent
The aqueous solution of base sodium cellulosate is mixed to form binder with butadiene-styrene rubber, carbon nano-fiber product is adhered on copper foil, then
It is dried in vacuum drying chamber, lithium ion cell electrode is made；Sodium carboxymethylcellulose and butylbenzene in the lithium ion cell electrode
The gross mass of rubber and the mass ratio of fiber cloth are 1~15: 100.
7. the application of carbon nano-fiber product prepared by method as described in claim 1 in lithium ion battery, by carbon Nanowire
It is dry after fiber products cut-parts, then it is assembled in button cell as lithium ion battery negative material；It is characterized in that carbon is received
The assembling of battery is directly carried out after rice fibre drying.
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| CN107305949A (en) * | 2016-04-25 | 2017-10-31 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of porous graphite negative material and preparation method and application |
| CN106654120A (en) * | 2016-12-09 | 2017-05-10 | 华南理工大学 | Carbon fibers used for direct methanol fuel cell and preparation method thereof |
| CN106654208B (en) * | 2016-12-21 | 2018-07-24 | 深圳市沃特玛电池有限公司 | A kind of preparation method of lithium iron phosphate battery negative electrode material |
| CN106865538A (en) * | 2017-03-10 | 2017-06-20 | 江苏海能动力科技有限公司 | A kind of carbon nanocoils material and preparation method thereof |
| CN107881600B (en) * | 2017-09-18 | 2020-05-19 | 大连理工大学 | Preparation method and application of nano carbon fiber for lithium ion battery cathode |
| CN108598474B (en) * | 2018-04-24 | 2019-07-05 | 湖北工程学院 | A kind of high-energy density lithium battery lithium iron phosphate positive material and preparation method thereof |
| CN110444742B (en) * | 2019-07-02 | 2022-04-15 | 天津大学 | Potassium-sulfur battery electrode material and preparation method and application thereof |
| 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 |
| CN113690546A (en) * | 2021-07-21 | 2021-11-23 | 华南理工大学 | Lithium-sulfur battery diaphragm and preparation method and application thereof |
| CN114256441B (en) * | 2021-11-16 | 2023-01-06 | 东莞市加伏锂电材料有限公司 | Lithium-carbon composite negative electrode, preparation method thereof and lithium battery |
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| CN102560889B (en) * | 2012-01-05 | 2014-04-02 | 黑龙江大学 | Method for producing bead-stringed PAN (polyacrylonitrile)-based carbon fiber electrode materials by electrostatic spinning |
| CN104409738A (en) * | 2014-11-05 | 2015-03-11 | 中国科学院金属研究所 | Making method of conductive carbon black/nanometer carbon fiber composite electrode for all-vanadium redox flow battery |
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