CN107195894A - A kind of metal carbon nano-fiber composite material and its preparation method and application - Google Patents
A kind of metal carbon nano-fiber composite material and its preparation method and application Download PDFInfo
- Publication number
- CN107195894A CN107195894A CN201710546201.5A CN201710546201A CN107195894A CN 107195894 A CN107195894 A CN 107195894A CN 201710546201 A CN201710546201 A CN 201710546201A CN 107195894 A CN107195894 A CN 107195894A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- metal
- composite material
- citrate
- fiber composite
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of metal carbon nano-fiber composite material and its preparation method and application, which solving metal carbon nano-fiber composite material in the relatively low technical problem of the amount of being spun into of metal active material in current material, the present invention includes carbon nano-fiber and bulk metal active material；The surface of bulk metal active material is by the carbon coating of polymer matrix, and internal is nanometer spherical material；Bulk metal active material is drawn by carbon nano-fiber and wound by carbon nano-fiber；The mass fraction that metal active material accounts for metal carbon nano-fiber composite material is 30~70%.Invention also provides its preparation method and application.The present invention can be used for the preparation field of battery material.
Description
Technical field
The present invention relates to battery material field, a kind of metal carbon nano-fiber composite material and its preparation are related in particular to
Methods and applications.
Background technology
In the last few years, the shortage of petroleum resources and increasingly sharpening for environmental problem, forced people to develop some more clear
Clean and efficient energy storage device.In all energy storage devices, lithium ion battery is because of spies such as its high-energy-density, long circulation lifes
Put and be widely used.But because the reserves of whole world lithium metal are limited, researcher starts to develop such as sodium-ion battery, magnesium
The energy storage devices such as ion battery, aluminium ion battery.At the same time, people are gradually diversified for the demand of energy storage device, flexible
The research and development of electrode material are into an important scientific research task.
Electrostatic spinning has that preparation facilities is simple, cost is low, can woven material is more, process controllability is strong, easy industrialization promotion
The advantages of.In the research of related to flexible electrode material, method of electrostatic spinning as prepare flexible electrode material means by
The extensive concern of people is arrived.
At present, the research on method of electrostatic spinning focuses primarily upon the inside that metal active material is scattered in fiber, obtains
To carbon nano-fiber composite material.The problem of most of electrode material volumetric expansion is big can be solved by the above method, simultaneously
The electric conductivity of material can be increased, be conducive to improving the chemical property of electrode material.
But the amount of being spun into of such a method metal active material is relatively low, and method of electrostatic spinning is for the selecting of solution system, quiet
There is higher requirement, microstructure of the external condition to product in terms of the selection of setting and the heat treatment of Electrospun parameter
Also there is large effect, it is still necessary to the problem of substantial amounts of research is to overcome existing.At present, both at home and abroad using the research of classical spinning
The inside that nano material is scattered in fiber is focused primarily upon, carbon nano-fiber composite material is obtained, rarely had micro-meter scale material
Expect the report combined with method of electrostatic spinning.
The content of the invention
The present invention is exactly that there is provided one for the relatively low technical problem of the amount of being spun into for solving metal active material in current material
Kind by the way that the material of micro-meter scale is carried out into electrostatic spinning, obtain metal carbon nano-fiber composite material and preparation method thereof and should
With.
Therefore, the present invention provides a kind of metal carbon nano-fiber composite material, metal carbon nano-fiber composite material includes
Carbon nano-fiber and metal active material, the surface of the bulk metal active material are and internal by the carbon coating of polymer matrix
For nanometer spherical material；Bulk metal active material is drawn by carbon nano-fiber and wound by carbon nano-fiber simultaneously；Metal
The metal active material mass fraction of carbon nano-fiber composite material is 30~70%.
It is preferred that, metal active material be ironic citrate, bismuth citrate, citric acid cobalt, ferric citrate, citric acid nickel,
Shape after one or more of carbonizations in zinc citrate, Titanium Citrate, citric acid zirconium, citric acid tin, magnesium citrate or copper citrate
Into material.
It is preferred that, polymer is in polyvinylpyrrolidone, polyacrylonitrile, polypyrrole, polyimides or polyvinyl alcohol
One or two combination.
Invention also provides a kind of preparation method of metal carbon nano-fiber composite material, it comprises the following steps：
(1) electrostatic spinning solution is configured：1~10wt% polymer is added in organic solution, is put into 60~90 DEG C of baking oven permanent
Temperature processing 3~30 hours, adds metal precursor, then stirs 4~24 hours, and electrostatic spinning solution, metal front is made
The ratio between weight ratio of body and polymer is (0.5~10)：1；(2) composite nano-fiber membrane is prepared using electrospinning process：Make
Electrospinning process parameter：Syringe needle internal diameter is 0.9~1.6mm, and temperature is 15~40 DEG C, relative humidity<30%,
Electrostatic potential is 15~22kV, and spinning solution flow is 0.4~1.5ml/h, and it is 15~30cm to receive distance, and rotating cylinder rotating speed is 500
~1200rpm, using single needle or Multi needle spinning；(3) it is heat-treated：The composite nano-fiber membrane that the step (2) is obtained exists
Nitrogen atmosphere, it is heat-treated at 600~1000 DEG C, programming rate is 1~10 DEG C/min, and cooling rate is 1~10 DEG C/min,
Soaking time is 1~5 hour, produces final product.
It is preferred that, the polymer of step (1) is polyvinylpyrrolidone, polyacrylonitrile, polypyrrole, polyimides or poly- second
One or both of enol is combined.
It is preferred that, the solvent of step (1) is absolute ethyl alcohol, propylene carbonate, ethyl acetate, butylene carbonic ester, N, N- bis-
One or more combinations in methylacetamide, N,N-dimethylformamide or 1-METHYLPYRROLIDONE.
It is preferred that, the metal precursor of step (1) is ironic citrate, bismuth citrate, citric acid cobalt, ferric citrate, lemon
One or more groups in lemon acid nickel, zinc citrate, Titanium Citrate, citric acid zirconium, citric acid tin, magnesium citrate or copper citrate
Close.
It is preferred that, the metal precursor of step (1) is the particle of micro-meter scale, and it is in a dimension, two dimensions or three
It is micron-scale in individual dimension.
Present invention simultaneously provides application of the metal carbon nano-fiber composite material as anode or negative material.
It is preferred that, applied to one kind in lithium ion battery, sodium-ion battery, Zinc ion battery or Magnesium ion battery or several
Kind.
The present invention has advantages below：
(1) material of micro-meter scale is carried out electrostatic spinning by the present invention, has obtained a kind of battery material with new construction.
The amount of being spun into for causing active material of this method is greatly improved, and can reach more than 65%.The structure of composite
The material that feature is mainly micro-meter scale is appeared in outside carbon nano-fiber, and surface is internal by the carbon coating of one layer of polymeric base
Material is changed into nano material after carbonization.The two ends of block are by two carbon nano-fiber tractions and by remaining carbon nanometer simultaneously
Fiber is wound, and realizes duplicate protection.The structure can provide more ions and electron propagation ducts for material, have simultaneously
Beneficial to the infiltration of electrolyte so that electrode material has preferable chemical property.
(2) present invention is prepared for composite nano-fiber membrane using electrostatic spinning as method, and material can be used as without conductive agent and glue
The flexible electrode material of knot agent is used.Present invention process is simple, controllability is strong, with low cost, low-carbon environment-friendly, is easy to industrialization to push away
Wide application.
Brief description of the drawings
Fig. 1 is the optical photograph of flexible electrode material prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention 1；
Fig. 3 is the transmission electron microscope picture of the embodiment of the present invention 1；
Fig. 4 is that the product of the embodiment of the present invention 1 is used as the cyclic discharge capacity figure of negative electrode of lithium ion battery.
Embodiment
The present invention will be further elaborated for example below, and subordinate's explanation is only for explaining the present invention, not to it
Content is defined.
Embodiment 1
Configure electrostatic spinning solution：1g polyacrylonitrile is added in 10g DMF solution, 60 are put into
DEG C baking oven in constant temperature handle 30 hours, add the bismuth citrate of 1.9g micro-meter scales, then stir 24 hours, be made electrostatic
The mass ratio of spinning solution, metal precursor and polymer is 1.9：1；
Composite nano-fiber membrane is prepared using electrostatic spinning process：Electrostatic spinning solution is poured into band internal diameter 1.2mm syringe needles
Syringe in, in room temperature relative humidity<It is small with 20kV voltage 1ml/h injection speed electrostatic spinning 8 in 30% environment
When, it is 20cm to receive distance, and rotating cylinder rotating speed is 1000rpm, and composite nano-fiber membrane is made；
Technology for Heating Processing：Obtained composite nano-fiber membrane is heat-treated at nitrogen atmosphere, 600 DEG C, heating speed
Spend for 3 DEG C/min, soaking time is 2 hours, produces final compound carbon nanofiber film；
Electro-chemical test：Product is cut into diameter 12mm disk, lithium ion battery is assembled, electro-chemical test is carried out.
Embodiment 2
Configure electrostatic spinning solution：0.5g polyacrylonitrile is added in 5g propylene carbonate solution, 60 DEG C of baking is put into
Constant temperature is handled 20 hours in case, adds the ironic citrate of 5g micro-meter scales, is then stirred 24 hours, electrostatic spinning is made molten
Liquid, metal precursor and polymer the ratio between be 10：1；
Composite nano-fiber membrane is prepared using electrostatic spinning process：Electrostatic spinning solution is poured into band internal diameter 0.9mm syringe needles
Syringe in, in room temperature relative humidity<In 30% environment, with 22kV voltage 0.8ml/h injection speed electrostatic spinning 6
Hour, it is 30cm to receive distance, and rotating cylinder rotating speed is 1200rpm, and composite nano-fiber membrane is made；
Technology for Heating Processing：Obtained composite nano-fiber membrane is heat-treated at nitrogen atmosphere, 1000 DEG C, heating speed
Spend for 5 DEG C/min, soaking time is 5 hours, produces final compound carbon nanofiber film；
Electro-chemical test：Product is cut into diameter 12mm disk, lithium ion battery is assembled, electro-chemical test is carried out.
Embodiment 3
Configure electrostatic spinning solution：5g polyvinylpyrrolidone is added in 10g DMA solution,
It is put into constant temperature in 90 DEG C of baking oven to handle 12 hours, adds the citric acid molybdenum of 2.5g micro-meter scales, then stir 4 hours, system
Electrostatic spinning solution, metal precursor and polymer the ratio between be 0.5：1；
Composite nano-fiber membrane is prepared using electrostatic spinning process：Electrostatic spinning solution is poured into band internal diameter 1.6mm syringe needles
Dual-head injector in, in room temperature relative humidity<In 30% environment, with 22kV voltage 0.4ml/h injection speed electrostatic
Spinning 10 hours, it is 15cm to receive distance, and rotating cylinder rotating speed is 500rpm, and composite nano-fiber membrane is made；
Technology for Heating Processing：Obtained composite nano-fiber membrane is heat-treated at nitrogen atmosphere, 800 DEG C, heating speed
Spend for 10 DEG C/min, soaking time is 1 hour, produces final compound carbon nanofiber film；
Electro-chemical test：Product is cut into diameter 12mm disk, sodium-ion battery is assembled, electro-chemical test is carried out.
Embodiment 4
Configure electrostatic spinning solution：2.74g polyvinylpyrrolidone is added into 8g N,N-dimethylformamide solution
In, it is put into constant temperature in 80 DEG C of baking oven and handles 3 hours, add the bismuth citrate of 1.37g micro-meter scales, then stirs 12 small
When, be made electrostatic spinning solution, metal precursor and polymer the ratio between be 0.5：1；
Composite nano-fiber membrane is prepared using electrostatic spinning process：Electrostatic spinning solution is poured into band internal diameter 1.0mm syringe needles
Syringe in, in room temperature relative humidity<In 30% environment, with 22kV voltage 0.9ml/h injection speed electrostatic spinning
10 hours, it was 15cm to receive distance, and rotating cylinder rotating speed is 500rpm, and composite nano-fiber membrane is made；
Technology for Heating Processing：Obtained composite nano-fiber membrane is heat-treated at nitrogen atmosphere, 600 DEG C, heating speed
Spend for 1 DEG C/min, soaking time is 4 hours, produces final compound carbon nanofiber film；
Electro-chemical test：Product is cut into diameter 12mm disk, Magnesium ion battery is assembled, electro-chemical test is carried out.
Embodiment 5
Configure electrostatic spinning solution：1 polyvinylpyrrolidone is added in 10g DMF solution, put
Enter constant temperature in 80 DEG C of baking oven to handle 3 hours, add 3.6g citric acid nickel, then stir 12 hours, electrostatic spinning is made molten
Liquid, metal precursor and polymer the ratio between be 3.6：1；
Composite nano-fiber membrane is prepared using electrostatic spinning process：Electrostatic spinning solution is poured into band internal diameter 1.2mm syringe needles
Syringe in, in room temperature relative humidity<In 30% environment, with 20kV voltage 0.8ml/h injection speed electrostatic spinning 8
Hour, it is 15cm to receive distance, and rotating cylinder rotating speed is 500rpm, and composite nano-fiber membrane is made；
Technology for Heating Processing：Obtained composite nano-fiber membrane is heat-treated at nitrogen atmosphere, 700 DEG C, heating speed
Spend for 5 DEG C/min, soaking time is 3 hours, produces final compound carbon nanofiber film；
Electro-chemical test：Product is cut into diameter 12mm disk, lithium ion battery is assembled, electro-chemical test is carried out.
Claims (10)
1. a kind of metal carbon nano-fiber composite material, it is characterized in that it includes carbon nano-fiber and bulk metal active material；
The surface of the bulk metal active material is by the carbon coating of polymer matrix, and internal is nanometer spherical material；The block gold
Category active material is drawn by the carbon nano-fiber and wound by the carbon nano-fiber；The metal active material accounts for described
The mass fraction of metal carbon nano-fiber composite material is 30~70%.
2. metal carbon nano-fiber composite material according to claim 1, it is characterised in that the active material of the bulk metal
Expect for ironic citrate, bismuth citrate, citric acid cobalt, ferric citrate, citric acid nickel, zinc citrate, Titanium Citrate, citric acid
The material formed after one or more of carbonizations in zirconium, citric acid tin, magnesium citrate or copper citrate.
3. metal carbon nano-fiber composite material according to claim 1, it is characterised in that the polymer is polyethylene
One or both of pyrrolidones, polyacrylonitrile, polypyrrole, polyimides or polyvinyl alcohol are combined.
4. a kind of preparation method of metal carbon nano-fiber composite material, it is characterized in that comprising the following steps：
(1) electrostatic spinning solution is configured：1~10wt% polymer is added in organic solution, 60~90 DEG C of baking oven is put into
Middle constant temperature is handled 3~30 hours, adds metal precursor, is then stirred 4~24 hours, and electrostatic spinning solution, metal is made
The mass ratio of presoma and polymer is (0.5~10)：1；
(2) composite nano-fiber membrane is prepared using electrospinning process：The electrospinning process parameter used：In syringe needle
Footpath is 0.9~1.6mm, and temperature is 15~40 DEG C, relative humidity<30%, electrostatic potential is 15~22kV, and spinning solution flow is
0.4~1.5ml/h, it is 15~30cm to receive distance, and rotating cylinder rotating speed is 500~1200rpm, using single needle or Multi needle spinning；
(3) it is heat-treated：The composite nano-fiber membrane that the step (2) is obtained carries out heat at nitrogen atmosphere, 600~1000 DEG C
Processing, programming rate is 1~10 DEG C/min, and cooling rate is 1~10 DEG C/min, and soaking time is 1~5 hour, is produced final
Product.
5. the preparation method of metal carbon nano-fiber composite material according to claim 4, it is characterised in that the step
(1) polymer is one or both of polyvinylpyrrolidone, polyacrylonitrile, polypyrrole, polyimides or polyvinyl alcohol
Combination.
6. the preparation method of metal carbon nano-fiber composite material according to claim 4, it is characterised in that the step
(1) solvent is absolute ethyl alcohol, propylene carbonate, ethyl acetate, butylene carbonic ester, DMAC N,N' dimethyl acetamide, N, N- diformazans
One or more combinations in base formamide or 1-METHYLPYRROLIDONE.
7. the preparation method of metal carbon nano-fiber composite material according to claim 4, it is characterised in that the step
(1) metal precursor is ironic citrate, bismuth citrate, citric acid cobalt, ferric citrate, citric acid nickel, zinc citrate, lemon
One or more combinations in sour titanium, citric acid zirconium, citric acid tin, magnesium citrate or copper citrate.
8. the preparation method of metal carbon nano-fiber composite material according to claim 4, it is characterised in that the step
(1) metal precursor is the particle of micro-meter scale, and it is micron-scale in a dimension, two dimensions or three dimensions.
9. metal carbon nano-fiber composite material as claimed in claim 1 is used as the application of anode or negative material.
10. metal carbon nano-fiber composite material according to claim 9 is as the application in anode or negative pole,
Characterized in that, applied to the one or more in lithium ion battery, sodium-ion battery, Zinc ion battery or Magnesium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546201.5A CN107195894B (en) | 2017-07-06 | 2017-07-06 | Metal carbon nanofiber composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546201.5A CN107195894B (en) | 2017-07-06 | 2017-07-06 | Metal carbon nanofiber composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107195894A true CN107195894A (en) | 2017-09-22 |
| CN107195894B CN107195894B (en) | 2020-06-09 |
Family
ID=59880414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710546201.5A Active CN107195894B (en) | 2017-07-06 | 2017-07-06 | Metal carbon nanofiber composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107195894B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767215A (en) * | 2018-05-15 | 2018-11-06 | 华中科技大学 | A kind of material and the preparation method and application thereof inhibiting zinc dendrite |
| CN108899487A (en) * | 2018-06-15 | 2018-11-27 | 合肥国轩高科动力能源有限公司 | A kind of high conductivity lithium ion battery negative material and preparation method thereof |
| CN109256280A (en) * | 2018-09-30 | 2019-01-22 | 天津工业大学 | A kind of stanniferous micro/nano structure doping carbon material and preparation method thereof |
| CN109305697A (en) * | 2018-08-27 | 2019-02-05 | 临沂大学 | A kind of preparation method of nitrogenous grading-hole carbon nano-tube film |
| CN109399691A (en) * | 2018-12-04 | 2019-03-01 | 江苏理工学院 | A kind of Cu-CuO/ carbon nano-fiber composite material and preparation method thereof |
| CN110048099A (en) * | 2019-03-28 | 2019-07-23 | 天津大学 | Electrode material of sodium-ion battery and its preparation method and application |
| CN111389403A (en) * | 2020-03-24 | 2020-07-10 | 福州大学 | Zn/Co doped carbon material and preparation method and application thereof |
| CN111939770A (en) * | 2020-08-03 | 2020-11-17 | 浙江大学 | Bismuth-based functional material for adsorbing gaseous iodine and preparation method and application thereof |
| CN113249824A (en) * | 2021-05-27 | 2021-08-13 | 陕西师范大学 | Preparation method of flexible carbon/lanthanum ferrite composite fiber membrane material |
| CN114507936A (en) * | 2020-10-28 | 2022-05-17 | 纳米及先进材料研发院有限公司 | Anisotropic heat-transfer electromagnetic interference shielding composite material and preparation method thereof |
| CN115538174A (en) * | 2022-12-02 | 2022-12-30 | 深圳市今朝时代股份有限公司 | High-performance electrode material for supercapacitor and supercapacitor made of high-performance electrode material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN102751475A (en) * | 2012-06-20 | 2012-10-24 | 天津大学 | Preparation for anode material of tin-cobalt alloy/carbon nanofiber film lithium ion battery |
| CN102965766A (en) * | 2012-11-14 | 2013-03-13 | 同济大学 | New method for synthesizing nanometal particle-loaded carbon nanofiber |
| CN103422192A (en) * | 2013-08-05 | 2013-12-04 | 江苏科技大学 | Fe-Co alloy/C composite nanofiber microwave absorbent, and preparation method and application thereof |
| CN103606689A (en) * | 2013-11-14 | 2014-02-26 | 清华大学 | Method for preparing carbon nanofiber based non-noble-metal catalyst through oxidation improved electrostatic spinning |
-
2017
- 2017-07-06 CN CN201710546201.5A patent/CN107195894B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101626075A (en) * | 2009-08-03 | 2010-01-13 | 北京化工大学 | Stannum and carbon composite nano-fiber film negative-electrode material and preparation method thereof |
| CN102751475A (en) * | 2012-06-20 | 2012-10-24 | 天津大学 | Preparation for anode material of tin-cobalt alloy/carbon nanofiber film lithium ion battery |
| CN102965766A (en) * | 2012-11-14 | 2013-03-13 | 同济大学 | New method for synthesizing nanometal particle-loaded carbon nanofiber |
| CN103422192A (en) * | 2013-08-05 | 2013-12-04 | 江苏科技大学 | Fe-Co alloy/C composite nanofiber microwave absorbent, and preparation method and application thereof |
| CN103606689A (en) * | 2013-11-14 | 2014-02-26 | 清华大学 | Method for preparing carbon nanofiber based non-noble-metal catalyst through oxidation improved electrostatic spinning |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108767215A (en) * | 2018-05-15 | 2018-11-06 | 华中科技大学 | A kind of material and the preparation method and application thereof inhibiting zinc dendrite |
| CN108767215B (en) * | 2018-05-15 | 2021-03-26 | 华中科技大学 | Material for inhibiting zinc dendrite and preparation method and application thereof |
| CN108899487A (en) * | 2018-06-15 | 2018-11-27 | 合肥国轩高科动力能源有限公司 | A kind of high conductivity lithium ion battery negative material and preparation method thereof |
| CN109305697A (en) * | 2018-08-27 | 2019-02-05 | 临沂大学 | A kind of preparation method of nitrogenous grading-hole carbon nano-tube film |
| CN109256280A (en) * | 2018-09-30 | 2019-01-22 | 天津工业大学 | A kind of stanniferous micro/nano structure doping carbon material and preparation method thereof |
| CN109256280B (en) * | 2018-09-30 | 2020-08-25 | 天津工业大学 | Tin-containing micro/nano-structure doped carbon material and preparation method thereof |
| CN109399691A (en) * | 2018-12-04 | 2019-03-01 | 江苏理工学院 | A kind of Cu-CuO/ carbon nano-fiber composite material and preparation method thereof |
| CN110048099A (en) * | 2019-03-28 | 2019-07-23 | 天津大学 | Electrode material of sodium-ion battery and its preparation method and application |
| CN111389403B (en) * | 2020-03-24 | 2022-11-15 | 福州大学 | Zn/Co doped carbon material and preparation method and application thereof |
| CN111389403A (en) * | 2020-03-24 | 2020-07-10 | 福州大学 | Zn/Co doped carbon material and preparation method and application thereof |
| CN111939770A (en) * | 2020-08-03 | 2020-11-17 | 浙江大学 | Bismuth-based functional material for adsorbing gaseous iodine and preparation method and application thereof |
| CN111939770B (en) * | 2020-08-03 | 2021-09-28 | 浙江大学 | Bismuth-based functional material for adsorbing gaseous iodine and preparation method and application thereof |
| CN114507936A (en) * | 2020-10-28 | 2022-05-17 | 纳米及先进材料研发院有限公司 | Anisotropic heat-transfer electromagnetic interference shielding composite material and preparation method thereof |
| CN114507936B (en) * | 2020-10-28 | 2023-04-14 | 纳米及先进材料研发院有限公司 | Anisotropic heat-transfer electromagnetic interference shielding composite material and preparation method thereof |
| CN113249824A (en) * | 2021-05-27 | 2021-08-13 | 陕西师范大学 | Preparation method of flexible carbon/lanthanum ferrite composite fiber membrane material |
| CN113249824B (en) * | 2021-05-27 | 2022-11-18 | 陕西师范大学 | Preparation method of flexible carbon/lanthanum ferrite composite fiber membrane material |
| CN115538174A (en) * | 2022-12-02 | 2022-12-30 | 深圳市今朝时代股份有限公司 | High-performance electrode material for supercapacitor and supercapacitor made of high-performance electrode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107195894B (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107195894A (en) | A kind of metal carbon nano-fiber composite material and its preparation method and application | |
| CN104289042B (en) | A kind of electrostatic spinning nano fiber electret filtering material and preparation method thereof | |
| Gao et al. | Recent progress and challenges in solution blow spinning | |
| Joshi et al. | Progress and potential of electrospinning-derived substrate-free and binder-free lithium-ion battery electrodes | |
| CN106848314B (en) | The lithium-sulfur cell preparation method of double-layer porous carbon nano-fiber and the method for preparing positive electrode using it | |
| CN106449159B (en) | The capacitor flexible electrode and preparation method of carbon fiber coated metal oxide | |
| CN104241661B (en) | Preparation method for combination electrode for all-vanadium redox flow battery | |
| Wang et al. | Recent progress of the preparation and application of electrospun porous nanofibers | |
| CN104392847B (en) | Preparation method of morphology controllable metal oxide/active carbon fiber combination electrode material | |
| CN104392845A (en) | Stretchable linear supercapacitor and lithium ion battery preparation method | |
| CN103194858A (en) | Elastomer composite with high dielectric constant and low dielectric loss and preparation method thereof | |
| CN106784745A (en) | The sodium-ion battery method for manufacturing electric spinning of cobaltosic oxide carbon nano-fiber | |
| CN104746236B (en) | A kind of polyimides/polyethylene glycol oxide cable-type composite nano-fiber membrane and preparation method thereof | |
| CN108193501A (en) | A kind of conductive shapes memory membrane, preparation method and its electric drive method | |
| CN1962429A (en) | Preparation method of pure nano-carbon tube film | |
| CN109727781A (en) | A kind of self-supporting flexible super capacitor electrode material and preparation method | |
| CN106935410A (en) | A kind of preparation method of the self-supporting flexible super capacitor based on graphitized ordered arrangement spinning fibre | |
| CN108666580A (en) | A kind of polymer three-dimensional collector, preparation method and application | |
| CN105040409A (en) | Preparation method for magnetic nanocomposite | |
| CN103757742B (en) | A kind of preparation method of nuclear shell structure nano fiber of fluorine-contained surface | |
| CN105200665B (en) | A kind of preparation method of lithium ion battery zinc germanate/carbon composite fibre negative material | |
| CN109904418A (en) | A kind of lithium ion battery negative material and preparation method thereof | |
| Lamberger et al. | Polymeric Janus Fibers | |
| CN113838680A (en) | Wearable full-flexible solid electrochromic supercapacitor and manufacturing method thereof | |
| CN113186656A (en) | Carbon nitride-polyvinyl alcohol composite antibacterial film and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |