CN105336921A - Preparation method and application of carbon nanofiber - Google Patents
Preparation method and application of carbon nanofiber Download PDFInfo
- Publication number
- CN105336921A CN105336921A CN201510623535.9A CN201510623535A CN105336921A CN 105336921 A CN105336921 A CN 105336921A CN 201510623535 A CN201510623535 A CN 201510623535A CN 105336921 A CN105336921 A CN 105336921A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- fibers
- fiber
- nano
- electrostatic spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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 invention discloses a preparation method of a porous graphitized carbon nanofiber product as a lithium ion battery negative electrode material and an application of the carbon nanofiber product in the lithium ion battery negative electrode material; with N,N-dimethyl formamide as a solvent and polyacrylonitrile as a high-molecular polymer, an electrostatic spinning solution is prepared. A morphology of the electrostatic spinning nanofiber is strengthened by preoxidation, PAN is converted to graphitized carbon through high temperature calcination in an argon gas atmosphere, and the calcined fiber is continued to be calcined in air to prepare the porous graphitized carbon nanofiber; the porous graphitized carbon nanofiber is used as the lithium ion battery negative electrode material, assembly and performance testing of a button-type battery are carried out, and the testing indicates that the porous graphitized carbon nanofiber as the lithium ion battery negative electrode material has excellent electrochemical performance.
Description
Technical field
The invention belongs to production technology and the application of material, be specifically related to a kind of technology of preparing of the carbon nano-fiber as lithium ion battery negative material.
Background technology
The positive electrode of the lithium ion battery of current commercialization mainly contains LiCoO
2, LiMn
2o
4, LiFePO
4and LiNiO
2deng, because graphite has reasonable price, the advantages such as chemical potential is low, it is business-like negative material main in the market.But the theoretical capacity of graphite is lower, is only 372mAhg
-1, and reached its theoretical capacity at present.At present, by carrying out modification for lithium ion battery material to carbonaceous material, the focus of research has been become.
Summary of the invention
The object of the invention is to propose a kind of preparation method that can be used for simple to operate, the repeatable strong carbon nano-fiber goods of lithium ion battery negative.
The present invention includes following sequential steps:
1) polyacrylonitrile (PAN) and DMF (DMF) are mixed with electrostatic spinning liquid;
2) electrostatic spinning liquid is carried out electrostatic spinning, obtain Electrospun nano-fibers;
3) Electrospun nano-fibers is weaved, obtain Electrospun nano-fibers cloth;
4) by the pre-oxidation of Electrospun nano-fibers cloth with the pattern of anchoring fiber;
5) by the Electrospun nano-fibers cloth high-temperature calcination in an inert atmosphere of pre-oxidation, polyacrylonitrile is converted into graphited C;
6) the graphited Electrospun nano-fibers cloth after high-temperature calcination is continued in air atmosphere calcining, obtain the graphited carbon nano-fiber goods with a large amount of hole.
The present invention has prepared nanofiber by method of electrostatic spinning, graphited carbon fiber has been obtained by further high-temperature calcination, calcine finally by air atmosphere, make the inside of fiber create more hole, this is conducive to the transmission of lithium ion and the raising of its chemical property.Can will have the graphited carbon nano-fiber of a large amount of hole as lithium ion battery negative material, this research is to promoting or improve carbonaceous material have certain impetus as the performance of lithium ion battery negative material.
Further, polyacrylonitrile of the present invention and N, the mixing quality ratio of dinethylformamide is 6 ~ 12: 100, and the viscosity of the electrostatic spinning liquid prepared with this proportioning is applicable to electrostatic spinning, coordinates the voltage of electrostatic spinning and receiving range to prepare the homogeneous Electrospun nano-fibers of pattern.
The voltage of electrostatic spinning of the present invention is 5 ~ 20kV, receiving range is 5 ~ 20cm, the internal diameter of electrostatic spinning syringe needle is 0.2 ~ 0.5mm, the fltting speed of electrostatic spinning liquid is 0.2 ~ 1.5mL/h, be attached to by aluminium foil on metal baffle or cylinder and receive Electrospun nano-fibers, drum rotation speed is 10 ~ 50r/min.The fiber continuity obtained is good, and fineness is stable, even.
Pre-oxidation of the present invention carries out in tube furnace, is placed in the middle part of boiler tube, passes into air with the flow of 1 ~ 6mL/min by pre-prepared precursor, with the programming rate of 1 ~ 2 DEG C/min, rises to 240 ~ 260 DEG C, and maintain 60 ~ 180min from normal temperature.Pre-oxidation is the pattern in order to anchoring fiber.Passing into a small amount of dry air is to ensure normal air exchange in preoxidation process.
High-temperature calcination described in step 5) of the present invention carries out in tube furnace, is arranged in quartz boat, is then placed in the middle part of boiler tube by the Electrospun nano-fibers of pre-oxidation, and pass into argon gas, with the programming rate of 3 ~ 7 DEG C/min, rise to 900 ~ 1200 DEG C from normal temperature, and maintain 60 ~ 150min.Under this hot conditions, PAN can be converted into the graphited carbon of high conductivity by calcining in an inert atmosphere.
Described in step 6) of the present invention, calcining carries out in tube furnace, Electrospun nano-fibers is arranged in quartz boat and is then placed in the middle part of boiler tube, the opening of tube furnace is threaded to maximum, or pass into air with the flow of 0 ~ 2mL/min, with the programming rate of 3 ~ 6 DEG C/min, rise to 350 ~ 450 DEG C from normal temperature, and maintain 120 ~ 1500min.The method by the part carbon removing in fiber, can prepare more lacunose graphited carbon nano-fiber.The air passed into is by the oxygen needed for the oxidation of guarantee material with carbon element, and its porous performance will be conducive to the diffusion of lithium ion, therefore be conducive to obtaining higher circulation volume and good cyclical stability.The pattern of nanofiber of the present invention is homogeneous, and the difference of foundation calcining heat and calcination time, the diameter of fiber is 100 ~ 400nm.
Another object of the present invention proposes the graphited carbon nano-fiber product application of concrete dynamic modulus prepared of said method in lithium ion battery.
By dry after the cut-parts of graphited for concrete dynamic modulus carbon nano-fiber goods, be then assembled in button cell as lithium ion battery negative material.
Because material with carbon element has the investigation and application widely that the characteristic such as good conductivity, raw material rich reserves obtains in electrochemical field, wherein graphite is the negative material of business-like lithium ion battery.This research plays certain impetus to having the commercialization of more high performance material with carbon element 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, with the solution of the 1-Methyl-2-Pyrrolidone of the Kynoar of 0.01 ~ 0.02g/mL for binding agent, carbon nano-fiber goods are adhered on Copper Foil, then dry in vacuum drying chamber, obtained lithium ion cell electrode; In described lithium ion cell electrode, the mass ratio of Kynoar and carbon nano-fiber goods is 2 ~ 15: 100.
2, be the ratio of 0.5 ~ 1: 1 in the mixing quality ratio of sodium carboxymethylcellulose and butadiene-styrene rubber, be that the aqueous solution and the butadiene-styrene rubber of the sodium carboxymethylcellulose of 0.5 ~ 2% is mixed to form binding agent by mass percent, carbon nano-fiber goods are adhered on Copper Foil, then dry at vacuum drying chamber, obtained lithium ion cell electrode; In described lithium ion cell electrode, the gross mass of sodium carboxymethylcellulose and butadiene-styrene rubber and the mass ratio of fiber cloth are 1 ~ 15: 100.
3, the assembling of battery is directly carried out after being dried by carbon nano-fiber goods.
Through the assembling of button cell, test shows: in the air atmosphere of 400 DEG C, calcine 3h through pre-oxidation and graphited nanofiber, and the graphited carbon nano-fiber of concrete dynamic modulus of 8h and 18h is at 0.5Ag
-1current density under charge and discharge cycles 100 enclose after its discharge capacity maintain 288.7 respectively, 366.8 and 452.0mAhg
-1, shown the cyclical stability that higher charge/discharge capacity is become reconciled.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of nanofiber of electrostatic spinning thing by preparing after pre-oxidation of preparation in embodiment one.
Fig. 2 is the partial enlarged drawing of Fig. 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of nanofiber of electrostatic spinning thing by preparing after pre-oxidation and graphitization of preparation in embodiment one.
Fig. 4 is the partial enlarged drawing of Fig. 3.
Fig. 5 be in embodiment one preparation electrostatic spinning thing by after pre-oxidation and graphitization, continue the scanning electron microscope (SEM) photograph calcining nanofiber prepared by 3h in air atmosphere.
Fig. 6 is the partial enlarged drawing of Fig. 5.
Fig. 7 be in embodiment one preparation electrostatic spinning thing by after pre-oxidation and graphitization, continue the scanning electron microscope (SEM) photograph calcining nanofiber prepared by 8h in air atmosphere.
Fig. 8 is the partial enlarged drawing of Fig. 7, and typical diameter is 252nm.
Fig. 9 be in embodiment one preparation electrostatic spinning thing by after pre-oxidation and graphitization, continue the scanning electron microscope (SEM) photograph calcining nanofiber prepared by 18h in air atmosphere.
Figure 10 is the partial enlarged drawing of Fig. 9.
Figure 11 is that the electrostatic spinning thing of preparation in embodiment one by calcining specific area (BET) resolution chart of nano wire fiber prepared by 3h with continuation after pre-oxidation and graphitization in air atmosphere.
Figure 12 is the transmission electron microscope picture of nanofiber of electrostatic spinning thing by preparing after pre-oxidation and graphitization of preparation in embodiment one.
Figure 13 is the partial enlarged drawing of Figure 12.
Figure 14 be in embodiment one preparation electrostatic spinning thing by after pre-oxidation and graphitization, continue the scanning electron microscope (SEM) photograph calcining nanofiber prepared by 18h in air atmosphere.
Figure 15 is the partial enlarged drawing of Figure 14.
Figure 16 be in embodiment one preparation electrostatic spinning thing by after pre-oxidation and graphitization, continue to calcine 3h in air atmosphere, nanofiber prepared by 8h and 18h as lithium ion battery electrode material at 0.5Ag
-1current density under charge-discharge performance curve.
Embodiment
One, the preparation method of the graphited carbon nano-fiber goods of concrete dynamic modulus:
1, the preparation of spinning solution: add 1.0g polyacrylonitrile (PAN) and 9.0gN in 25mL conical flask, dinethylformamide (DMF), normal temperature magnetic agitation 12 ~ 36h, prepares homogeneous electrostatic spinning liquid.
2, electrostatic spinning: syringe spinning solution being poured into 10mL capacity, puts into electrostatic spinning apparatus, aluminium foil is attached to metal
Baffle plate collects Electrospun nano-fibers, and voltage is set to 13 ~ 17KV, and receiving range is 10 ~ 18cm, carries out electrostatic spinning, obtains Electrospun nano-fibers.
3, weave: machine on Electrospun nano-fibers is weaved, obtain Electrospun nano-fibers cloth.
4, pre-oxidation: after Electrospun nano-fibers cloth is cut into fritter, puts into quartz boat, be placed in tube furnace, pass into the dry air of low discharge, flow velocity is 1 ~ 6mL/min, is warming up to 240 ~ 260 DEG C, and maintains 60 ~ 180min with the heating rate of 1 ~ 2 DEG C/min.
5, the preparation of graphited carbon nano-fiber: the electrospun fibers cloth after pre-oxidation is put into tube furnace, pass into the high-purity argon gas of low discharge, flow velocity is 1 ~ 6mL/min, with the programming rate of 3 ~ 7 DEG C/min, rise to 1000 DEG C from normal temperature and maintain 60 ~ 150min, PAN is converted into graphited carbon.
6, the preparation of concrete dynamic modulus graphited carbon nano-fiber goods: graphited electrospun fibers cloth is put into quartz boat and is positioned over tube furnace middle part, the opening of tube furnace be threaded to maximum or pass into certain air with the speed of 0 ~ 2mL/min, with the programming rate of 3 ~ 6 DEG C/min, 400 DEG C are risen to from normal temperature, and maintain 120 ~ 1500min, prepare the graphited carbon nano-fiber goods of concrete dynamic modulus.
Two, the material of preparation is carried out the assembling of lithium ion battery as lithium ion battery negative material goods:
Graphited for concrete dynamic modulus carbon nano-fiber goods are cut to the size of battery pole piece as lithium ion battery negative material goods, dry 8 ~ 16h in the vacuum drying chamber of 60 ~ 120 DEG C (preferably 80 DEG C), to remove a small amount of moisture in fiber.
Due to the difference of fibre plate thickness in the present invention, the quality of the fibre plate after cutting be 1 ~ 8mg not etc.Directly as lithium ion battery anode active material after weighing, carry out the assembling of 2032 model button cells.
Carried out the assembling of battery by following 3 kinds of modes, can assemble and obtain lithium ion battery negative material.
1, with the solution of the 1-Methyl-2-Pyrrolidone of the Kynoar of 0.01g/mL (PVDF) (NMP) for binding agent, fibre is adhered on Copper Foil, then dries in vacuum drying chamber, obtained lithium ion cell electrode.In the lithium ion cell electrode made, the mass ratio of Kynoar (PVDF) and fiber cloth is 2 ~ 15: 100.
2, be the ratio of 0.5 ~ 1: 1 in mixing quality ratio, the aqueous solution of sodium carboxymethylcellulose (CMC) and the butadiene-styrene rubber (SBR) that containing mass percent are 0.5 ~ 2% are mixed to form binding agent, fibre is adhered on Copper Foil, then dry in vacuum drying chamber, obtained lithium ion cell electrode.In the described lithium ion cell electrode made, the gross mass of sodium carboxymethylcellulose (CMC) and butadiene-styrene rubber (SBR) and the mass ratio of fiber cloth are 1 ~ 15: 100.
3, by dried fibre do not add binding agent and without the mode condition of Copper Foil under directly carry out the assembling of battery.
After dried fibre grinding, the carbon black of spinning fibre mass fraction 0 ~ 15% is added again as conductive additive according to the proportioning of above-mentioned binding agent, electrode material through stirring, being coated with and dry continues to be placed in the dry 6 ~ 24h of baking oven of 120 DEG C, then proceed to rapidly in glove box, carry out the assembling of button cell.
Be to electrode with lithium sheet, the calculating of the size of charging and discharging currents is with the quality of the graphited carbon nano-fiber goods of concrete dynamic modulus for foundation, and voltage range 0.01 ~ 3.0V, passes through 0.5Ag
-1the concrete dynamic modulus graphited carbon nano-fiber goods charge and discharge cycles 100 of current density to calcination time different in air atmosphere enclose the stability investigating its performance and circulation.
Three, performance characterization:
Fig. 1 is the scanning electron microscope (SEM) photograph of the electrospun fibers nanofiber prepared by pre-oxidation 2h under 250 DEG C of conditions prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one.Fig. 2 is the partial enlarged drawing of Fig. 1, the 391nm of the typical diameter of nanofiber.
Fig. 3 is that the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one after pre-oxidation 2h, calcines the scanning electron microscope (SEM) photograph of fiber prepared by 2h under 250 DEG C of conditions in the Ar atmosphere of 1000 DEG C.Fig. 4 is its partial enlarged drawing.Wherein the diameter of fiber is significantly less than the diameter of the fiber by 250 DEG C of pre-oxidation, and representational diameter is 340nm.
Fig. 5 is that the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one is under 250 DEG C of conditions after pre-oxidation 2h, in the Ar atmosphere of 1000 DEG C, calcine 2h, continue the scanning electron microscope (SEM) photograph calcining nanofiber prepared by 3h in the air atmosphere of 400 DEG C.Fig. 6 is the partial enlarged drawing of Fig. 5.
Fig. 7 is that the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one is under 250 DEG C of conditions after pre-oxidation 2h, in the Ar atmosphere of 1000 DEG C, calcine 2h, continue the scanning electron microscope (SEM) photograph calcining nanofiber prepared by 8h in the air atmosphere of 400 DEG C.Fig. 8 is the partial enlarged drawing of Fig. 7, and typical diameter is 252nm.
Fig. 9 is that the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one is under 250 DEG C of conditions after pre-oxidation 2h, in the Ar atmosphere of 1000 DEG C, calcine 2h, continue the scanning electron microscope (SEM) photograph calcining nanofiber prepared by 18h in the air atmosphere of 400 DEG C.Figure 10 is the partial enlarged drawing of Fig. 9, and representative diameter is 217nm, and this shows, along with long calcining in the air of 400 DEG C, the diameter of fiber has reduction to a certain degree.
Figure 11 is that the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one after pre-oxidation 2h, calcines nanofiber prepared by 2h and the specific area resolution chart continuing to calcine nanofiber prepared by 3h in the air atmosphere of 400 DEG C under 250 DEG C of conditions in the Ar atmosphere of 1000 DEG C.By finding out in figure, after graphited carbon nano-fiber passes through to calcine 3h in the air atmosphere of 400 DEG C, its specific area has had larger lifting, is respectively 40.6 and 542.6m by calculating its value
2/ g.
Figure 12 after pre-oxidation 2h, calcines the transmission electron microscope picture of nanofiber prepared by 2h for the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one under 250 DEG C of conditions in the Ar atmosphere of 1000 DEG C.Figure 13 is the partial enlarged drawing of Figure 12, and its color is comparatively dark, shows that the porosity in fiber is less.
Figure 14 is that the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one is under 250 DEG C of conditions after pre-oxidation 2h, in the Ar atmosphere of 1000 DEG C, calcine 2h, continue the transmission electron microscope picture calcining nanofiber prepared by 18h in the air atmosphere of 400 DEG C.Figure 15 is the partial enlarged drawing of Figure 14, and its color is more shallow, shows that the porosity in fiber is larger.
Figure 16 is that the electrospun fibers prepared under 15KV voltage for spinning solution with 1.0gPAN and 9.0gDMF in embodiment one is under 250 DEG C of conditions after pre-oxidation 2h, 2h is calcined in the Ar atmosphere of 1000 DEG C, continue in the air atmosphere of 400 DEG C, calcine 3h, nanofiber prepared by 8h and 18h directly as electrode material at 0.5Ag
-1current density under charge-discharge performance figure, after 100 circle circulations, its discharge capacity is respectively: 288.7,366.8 and 452.0mAh/g, show higher capacity and good cyclical stability.This shows, porosity has very important effect to the nanofiber of preparation as the performance of li-ion electrode materials.
Claims (10)
1. a preparation method for carbon nano-fiber goods, is characterized in that comprising following sequential steps:
1) polyacrylonitrile and DMF are mixed with electrostatic spinning liquid;
2) electrostatic spinning liquid is carried out electrostatic spinning, obtain Electrospun nano-fibers;
3) Electrospun nano-fibers is weaved, obtain Electrospun nano-fibers cloth;
4) by the pre-oxidation of Electrospun nano-fibers cloth with the pattern of anchoring fiber;
5) by the Electrospun nano-fibers cloth high-temperature calcination in an inert atmosphere of pre-oxidation, polyacrylonitrile is converted into graphited C;
6) the graphited Electrospun nano-fibers cloth after high-temperature calcination is continued in air atmosphere calcining, obtain the graphited carbon nano-fiber goods with a large amount of hole.
2. preparation method according to claim 1, is characterized in that described polyacrylonitrile is 6 ~ 12: 100 with the mixing quality ratio of DMF.
3. preparation method according to claim 1, it is characterized in that the voltage of described electrostatic spinning is 5 ~ 20kV, receiving range is 5 ~ 20cm, the internal diameter of electrostatic spinning syringe needle is 0.2 ~ 0.5mm, the fltting speed of electrostatic spinning liquid is 0.2 ~ 1.5mL/h, be attached to by aluminium foil on metal baffle or cylinder and receive Electrospun nano-fibers, drum rotation speed is 10 ~ 50r/min.
4. preparation method according to claim 1, it is characterized in that described pre-oxidation carries out in tube furnace, pre-prepared precursor is placed in the middle part of boiler tube, air is passed into the flow of 1 ~ 6mL/min, with the programming rate of 1 ~ 2 DEG C/min, rise to 240 ~ 260 DEG C from normal temperature, and maintain 60 ~ 180min.
5. preparation method according to claim 1, it is characterized in that high-temperature calcination described in step 5) carries out in tube furnace, the Electrospun nano-fibers of pre-oxidation is arranged in quartz boat, then be placed in the middle part of boiler tube, and pass into argon gas, with the programming rate of 3 ~ 7 DEG C/min, rise to 900 ~ 1200 DEG C from normal temperature, and maintain 60 ~ 150min.
6. preparation method according to claim 1, it is characterized in that described in step 6), calcining carries out in tube furnace, Electrospun nano-fibers is arranged in quartz boat and is then placed in the middle part of boiler tube, the opening of tube furnace is threaded to maximum, or pass into air with the flow of 0 ~ 2mL/min, with the programming rate of 3 ~ 6 DEG C/min, rise to 350 ~ 450 DEG C from normal temperature, and maintain 120 ~ 1500min.
7. the application of carbon nano-fiber goods in lithium ion battery prepared of method as claimed in claim 1, by dry after the cut-parts of carbon nano-fiber goods, is then assembled in button cell as lithium ion battery negative material.
8. apply according to claim 7, it is characterized in that with the solution of the 1-Methyl-2-Pyrrolidone of the Kynoar of 0.01 ~ 0.02g/mL for binding agent, carbon nano-fiber goods are adhered on Copper Foil, then dries in vacuum drying chamber, obtained lithium ion cell electrode; In described lithium ion cell electrode, the mass ratio of Kynoar and carbon nano-fiber goods is 2 ~ 15: 100.
9. apply according to claim 7, it is characterized in that in the mixing quality ratio of sodium carboxymethylcellulose and butadiene-styrene rubber be the ratio of 0.5 ~ 1: 1, be that the aqueous solution and the butadiene-styrene rubber of the sodium carboxymethylcellulose of 0.5 ~ 2% is mixed to form binding agent by mass percent, carbon nano-fiber goods are adhered on Copper Foil, then dry at vacuum drying chamber, obtained lithium ion cell electrode; In described lithium ion cell electrode, the gross mass of sodium carboxymethylcellulose and butadiene-styrene rubber and the mass ratio of fiber cloth are 1 ~ 15: 100.
10. apply according to claim 7, it is characterized in that the assembling directly carrying out battery after being dried by carbon nano-fiber goods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510623535.9A CN105336921B (en) | 2015-09-28 | 2015-09-28 | A kind of preparation method and applications of carbon nano-fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510623535.9A CN105336921B (en) | 2015-09-28 | 2015-09-28 | A kind of preparation method and applications of carbon nano-fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105336921A true CN105336921A (en) | 2016-02-17 |
| CN105336921B CN105336921B (en) | 2018-07-20 |
Family
ID=55287321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510623535.9A Active CN105336921B (en) | 2015-09-28 | 2015-09-28 | A kind of preparation method and applications of carbon nano-fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105336921B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106654208A (en) * | 2016-12-21 | 2017-05-10 | 深圳市沃特玛电池有限公司 | Preparation method for negative electrode material of lithium iron phosphate battery |
| 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 |
| 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 |
| CN107881600A (en) * | 2017-09-18 | 2018-04-06 | 大连理工大学 | A kind of preparation method and applications of carbon nano-fiber for negative electrode of lithium ion battery |
| CN108598474A (en) * | 2018-04-24 | 2018-09-28 | 湖北工程学院 | A kind of high-energy density lithium battery lithium iron phosphate positive material and preparation method thereof |
| CN110444742A (en) * | 2019-07-02 | 2019-11-12 | 天津大学 | Potassium sulphur battery electrode material and its preparation method and application |
| 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 |
| CN114256441A (en) * | 2021-11-16 | 2022-03-29 | 东莞市加伏新材料研究院有限公司 | Lithium-carbon composite negative electrode, preparation method thereof and lithium battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560889A (en) * | 2012-01-05 | 2012-07-11 | 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 |
-
2015
- 2015-09-28 CN CN201510623535.9A patent/CN105336921B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560889A (en) * | 2012-01-05 | 2012-07-11 | 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 |
Non-Patent Citations (2)
| Title |
|---|
| JEANNE E PANELS ET AL.: "Synthesis and characterization of magnetically active carbon nanofiber/iron oxide composites with hierarchical pore structures", 《NANOTECHNOLOGY》 * |
| N. YUSOF ET AL.: "Post spinning and pyrolysis processes of polyacrylonitrile (PAN)-based carbon fiber and activated carbon fiber: A review", 《JOURNAL OF ANALYTICAL AND APPLIED PYROSIS》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106654208A (en) * | 2016-12-21 | 2017-05-10 | 深圳市沃特玛电池有限公司 | Preparation method for negative electrode material of lithium iron phosphate battery |
| 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 |
| CN107881600A (en) * | 2017-09-18 | 2018-04-06 | 大连理工大学 | A kind of preparation method and applications of carbon nano-fiber for negative electrode of lithium ion battery |
| 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 |
| CN108598474A (en) * | 2018-04-24 | 2018-09-28 | 湖北工程学院 | A kind of high-energy density lithium battery lithium iron phosphate positive material and preparation method thereof |
| CN110444742A (en) * | 2019-07-02 | 2019-11-12 | 天津大学 | Potassium sulphur battery electrode material and its preparation method and application |
| 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 |
| CN114256441A (en) * | 2021-11-16 | 2022-03-29 | 东莞市加伏新材料研究院有限公司 | Lithium-carbon composite negative electrode, preparation method thereof and lithium battery |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105336921B (en) | 2018-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105336921A (en) | Preparation method and application of carbon nanofiber | |
| CN105098172B (en) | The preparation method of porous graphite carbon coated ferriferrous oxide nanofiber article and its application in lithium ion battery | |
| CN109004205B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN109599546A (en) | Asphalt carbon-coated natural mixed graphite material and method for preparing lithium ion battery cathode by using same | |
| CN106941167A (en) | A kind of porous composite negative pole material of lithium ion battery and preparation method thereof | |
| WO2018006557A1 (en) | Tunable and scalable synthesis of hierarchical porous nanocarbon/sulfur composite cathodes | |
| TWI483448B (en) | Process for producing spherical lfp/c or lfpo/c composite material through spray drying method and use the same | |
| CN109065808B (en) | Preparation method of functional interlayer for lithium-sulfur battery | |
| CN110416503A (en) | A kind of soft carbon cladding titanium phosphate sodium mesoporous composite material and the preparation method and application thereof | |
| CN106129356B (en) | A kind of preparation method of hollow meso-porous titanium dioxide manganese pipe/sulphur composite material | |
| CN109390577A (en) | Si/SiO2/ C composite nano-fiber material and preparation method thereof and negative electrode material | |
| CN110331469A (en) | The preparation method and applications of CuO/Cu nitrogen-doped carbon nano-fiber material | |
| CN106328914A (en) | Method for preparing multi-shell-layer hollow stannic oxide material with carbon nano-microspheres as template and application of multi-shell-layer hollow stannic oxide material | |
| Chen et al. | Ultrafine MoO 2 nanoparticles encapsulated in a hierarchically porous carbon nanofiber film as a high-performance binder-free anode in lithium ion batteries | |
| CN112786869B (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material | |
| CN105742614A (en) | vanadium pentoxide positive electrode material and preparation method thereof | |
| Lv et al. | Carbon nanotube-embedded hollow carbon nanofibers as efficient hosts for advanced lithium–sulfur batteries | |
| CN105958030A (en) | Preparation method of positive electrode material of lithium-sulphur battery | |
| CN114530573B (en) | Flexible self-supporting positive electrode for sodium ion battery and preparation method and application thereof | |
| CN116081589A (en) | Lithium-rich lithium iron manganese phosphate material and preparation method thereof | |
| Yin et al. | A novel sulfur/carbon composite for low cost lithium–sulfur batteries with high cycling stability | |
| CN109449440A (en) | Ultra-thin soft carbon nanometer sheet of micropore and its preparation method and application | |
| CN110112398B (en) | LiCuVO4Preparation method of nano-fiber, product and application thereof | |
| CN111916725B (en) | Phosphorus-doped high-nickel cathode material for lithium battery and preparation process thereof | |
| CN113753962A (en) | Cobalt sulfide/carbon composite negative electrode material for sodium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |