CN103316594A - Preparation method of carbon-nanotube hollow fiber membranes - Google Patents
Preparation method of carbon-nanotube hollow fiber membranes Download PDFInfo
- Publication number
- CN103316594A CN103316594A CN2013102728004A CN201310272800A CN103316594A CN 103316594 A CN103316594 A CN 103316594A CN 2013102728004 A CN2013102728004 A CN 2013102728004A CN 201310272800 A CN201310272800 A CN 201310272800A CN 103316594 A CN103316594 A CN 103316594A
- Authority
- CN
- China
- Prior art keywords
- preparation
- wire
- cnt
- carbon nanotube
- fibre membrane
- 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
Images
Abstract
The invention belongs to the technical field of nano-material assembling, and relates to a preparation method of carbon-nanotube hollow fiber membranes. The method is characterized in that the preparation method is implemented through the following steps of: 1, acidifying carbon nanotubes in a concentrated acid solution, and introducing hydrophilic groups; 2, dispersing the acidified carbon nanotubes in monohydric alcohol, and depositing the carbon nanotubes on a metal template through electrophoretic deposition; 3, calcining and solidifying the obtained object under anaerobic conditions; and 4, removing the metal template, so that an independently self-supported carbon-nanotube hollow fiber membrane can be obtained. The method has the advantages that a preparation process is simple, no expensive equipment is required, and the method is flexible and controllable.
Description
Technical field
The present invention relates to a kind of preparation method of CNT hollow-fibre membrane, belong to the nanomaterial assembly technical field.
Background technology
CNT has outstanding physical chemistry, engineering properties, comprises excellent electrical and thermal conductivity performance, overstable chemical inertness, the specific area of super large, the mechanical strength of superelevation etc.Along with the development of nano material technology of preparing and perfect, the production cost of CNT constantly reduces.These factors all stimulating researchers attempt these invisible fiber fines be assembled into can be practical, high performance material, be incorporated in the macro object to the excellent properties Single Carbon Nanotubes.As typical monodimension nanometer material, add that it is antibiotic, the ability of antiacid alkali, CNT is the ideal material of preparation diffusion barrier.
At present, carbon nano-tube film mainly obtains by the method for vacuum filtration.Although this preparation method is simply efficient,, still there are some outstanding problems, be mainly manifested in: the one, the carbon nano-tube film of preparing mostly is the paper shape, and structure is single, is restricting it and is further developing; The 2nd,, the carbon nano-tube film of preparing is essential supporter in running, and this is just to the simplification of membrane module, and miniaturization is intensive very unfavorable.Comparatively speaking, hollow-fibre membrane is with its higher loading density, excellent self-supporting performance, larger membrane area in the unit volume and become the principal mode of membrane filtration.Therefore, development CNT hollow-fibre membrane is particularly important.But, yet there are no report about the technology of preparing of CNT hollow-fibre membrane.
Summary of the invention
The present invention mainly is the shortcoming that exists for existing CNT membrane preparation technology, and the CNT membrane structure of namely preparing is single, and operation needs supporter, is difficult to satisfy development need, and proposes a kind of preparation method of CNT hollow-fibre membrane.Preparation method proposed by the invention, technique is simple, need not expensive equipment, and method is controlled flexibly.
Basic conception of the present invention is that the CNT with acidifying utilizes electrophoretic deposition technique to be fixed on the metal matrix, removes metal matrix after high temperature is fixing and namely obtains full CNT hollow-fibre membrane.
Preparation method's step of a kind of CNT hollow-fibre membrane proposed by the invention is as follows:
(1) acidifying of CNT: CNT is placed in the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, under 40~80 ° of C, is incubated 2~6 hours.Then mixed liquor is diluted, and carbon nanotube separation out.
(2) electrophoretic deposition: the carbon nanotube dispersed after the acidifying in saturated monohydroxy alcohol, and is added the magnesium nitrate of 20~200mg/L.After this, this carbon nano tube dispersion liquid is poured in the electrodeposit reaction device.Wire is as masterplate, and as the negative electrode of electrophoretic deposition system.Voltage is set as 30~160V, and the electrophoretic deposition time is made as 1~10 minute, but successive sedimentation repeatedly.
(3) anaerobic calcining: after deposition process was finished, the wire that the surface is covered with carbon nanotube layer was calcined 0.5~4 hour under 200~1000 ° of C at oxygen free condition, naturally cooled to afterwards room temperature.
(4) remove template: the wire that is covered with carbon nanotube layer after will calcining is put into FeCl
3In/HCl the etching liquid, the wire that melts away can obtain the CNT hollow-fibre membrane of independent self-supporting, cleans to remove metal ion with a large amount of water at last.
Among the present invention, described in the step (1) in the nitration mixture volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid be 1:0~5.
Among the present invention, the separation method of CNT is vacuum filtration or high speed centrifugation described in the step (1).
Among the present invention, saturated monohydroxy alcohol is absolute ethyl alcohol, anhydrous isopropyl alcohol or anhydrous normal butyl alcohol described in the step (2).
Among the present invention, the dosage of magnesium nitrate is 20~200mg/L described in the step (2).
Among the present invention, described in the step (2) in the carbon nano tube dispersion liquid content of CNT be 100~500mg/L.
Among the present invention, wire described in the step (2) is iron wire, copper wire, aluminium wire, titanium silk or nickel wire.
Among the present invention, frequency of depositing is 1~20 time described in the step (2).
Among the present invention, oxygen free condition is vacuum or inert gas shielding described in the step (3).
Among the present invention, the etching liquid composition consists of 0.5~5mol/L FeCl described in the step (4)
3/ 0.1~1mol/LHCl.
Preparation technology of the present invention is simple, need not expensive equipment; Method is flexible, and the CNT hollow fiber film structure of preparation is controlled; The CNT hollow-fibre membrane agent structure of preparation is attractive in appearance, well-balanced.
Description of drawings
Fig. 1 is the ESEM picture of the different CNT hollow-fibre membrane side of 3 external diameters utilizing the technology that the present invention relates to prepare.The external diameter of 3 CNT hollow-fibre membranes from left to right is followed successively by 240 μ m among the figure, 295 μ m and 342 μ m.Fig. 2 utilizes the technology that the present invention relates to prepare the ESEM picture in CNT hollow-fibre membrane cross section.The external diameter of CNT hollow-fibre membrane is 465 μ m among the figure, internal diameter 150 μ m.
These ESEM pictures are to adopt Hitachi S-4800 type ESEM, at accelerating potential are to take under the condition of 10kV.
The specific embodiment
Further specify the preparation details of CNT hollow-fibre membrane below by specific embodiment, but the present invention not only is confined to following examples.
Embodiment 1:
Take copper wire as masterplate, isopropyl alcohol is that the preparation method of CNT hollow-fibre membrane of dispersant is as follows:
The first step takes by weighing the 1g CNT, and to pour the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid (volume ratio 1:3) into inner, is heated to 60 ℃, is incubated 3 hours.Then with the concentrated acid solution dilution, CNT is separated by vacuum filtration;
The carbon nanotube dispersed of second step after with the 100mg acidifying and adds the magnesium nitrate of 40mg in the 200mL isopropyl alcohol.The copper wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 160V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 6 times;
The 3rd step was put into tube type resistance furnace with the wire that the surface is covered with carbon nanotube layer, under 500 ℃ of the argon shields, calcined 1 hour, naturally cooled to afterwards room temperature;
The copper wire that is covered with carbon nanotube layer after the 4th step will calcine is put into 2.5mol/L FeCl
3In/0.5mol/LHCl the solution, copper wire melts away.The CNT hollow-fibre membrane that obtains cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 320 μ m.
Embodiment 2:
Take copper wire as masterplate, ethanol is that the preparation method of CNT hollow-fibre membrane of dispersant is as follows:
The first step takes by weighing the 1g CNT, and to pour the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid (volume ratio 1:2) into inner, is heated to 40 ℃, is incubated 4 hours.Then with the concentrated acid solution dilution, CNT is separated by 6000 rpms high speed centrifugation.
The carbon nanotube dispersed of second step after with the 100mg acidifying and adds the magnesium nitrate of 40mg in 200mL ethanol.The copper wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 160V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 6 times;
The 3rd step was put into tube type resistance furnace with the copper wire that the surface is covered with carbon nanotube layer, under 300 ℃ in the vacuum, calcined 1 hour, naturally cooled to afterwards room temperature;
The 4th step went on foot with the 4th among the embodiment 1.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 287 μ m.
Embodiment 3:
Take iron wire as masterplate, isopropyl alcohol is that the preparation method of CNT hollow-fibre membrane of dispersant is as follows:
The first step is with the first step among the embodiment 1;
The carbon nanotube dispersed of second step after with the 100mg acidifying and adds the magnesium nitrate of 40mg in the 200mL isopropyl alcohol.The iron wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 85V, and the electrophoretic deposition time is made as 8 minutes, successive sedimentation 6 times;
The 3rd step was put into tube type resistance furnace with the iron wire that the surface is covered with carbon nanotube layer, under 500 ℃ of the nitrogen protections, calcined 1 hour, naturally cooled to afterwards room temperature;
The iron wire that is covered with carbon nanotube layer after the 4th step will calcine is put into 2.5mol/L FeCl
3In/0.5mol/LHCl the solution, iron wire melts away.The CNT hollow-fibre membrane that obtains cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 245 μ m.
Embodiment 4:
Take iron wire as masterplate, n-butanol is that the preparation method of CNT hollow-fibre membrane of dispersant is as follows:
The first step is with the first step among the embodiment 2;
The carbon nanotube dispersed of second step after with the 100mg acidifying and adds the magnesium nitrate of 40mg in the 150mL n-butanol.The iron wire of diameter 150 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 85V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 8 times;
The 3rd step went on foot with the 3rd among the embodiment 3;
The iron wire that is covered with carbon nanotube layer after the 4th step will calcine is put into 3mol/L FeCl
3In/1mol/L HCl the solution, iron wire melts away.The full CNT hollow-fibre membrane that obtains cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 150 μ m, external diameter 298 μ m.
Embodiment 5:
Take aluminium wire as masterplate, isopropyl alcohol is that the preparation method of CNT hollow-fibre membrane of dispersant is as follows:
The first step is with the first step among the embodiment 1;
The carbon nanotube dispersed of second step after with the 100mg acidifying and adds the magnesium nitrate of 40mg in the 200mL isopropyl alcohol.The aluminium wire of diameter 450 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 160V, and the electrophoretic deposition time is made as 10 minutes, successive sedimentation 6 times;
The 3rd step was put into tube type resistance furnace with the aluminium wire that the surface is covered with carbon nanotube layer, under 500 ℃ of the argon shields, calcined 2 hours, naturally cooled to afterwards room temperature;
The aluminium wire that is covered with carbon nanotube layer after the 4th step will calcine is put into 2.5mol/L FeCl
3In/0.5mol/LHCl the solution, aluminium wire melts away.The CNT hollow-fibre membrane that obtains cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 450 μ m, external diameter 605 μ m.
Embodiment 6:
Take nickel wire as masterplate, isopropyl alcohol is that the preparation method of CNT hollow-fibre membrane of dispersant is as follows:
The first step is with the first step among the embodiment 1;
Second step in the 250mL isopropyl alcohol, adds the magnesium nitrate of 50mg with the 100mg carbon nanotube dispersed again.The nickel wire of diameter 450 μ m is as masterplate, and as the negative electrode of electrophoresis system.Voltage is set as 85V, and the electrophoretic deposition time is made as 10 minutes.Successive sedimentation 8 times;
The 3rd step was put into tube type resistance furnace with the nickel wire that the surface is covered with carbon nanotube layer, under 800 ℃ of the argon shields, calcined 30 hours, naturally cooled to afterwards room temperature;
The nickel wire that is covered with carbon nanotube layer after the 4th step will calcine is put into 2.5mol/L FeCl
3In/1mol/L HCl the solution, nickel wire melts away.The CNT hollow-fibre membrane that obtains cleans with a large amount of water.
Stereoscan photograph shows: the CNT hollow-fibre membrane of preparation has smooth well-balanced outer surface, and internal diameter is 450 μ m, external diameter 560 μ m.
Claims (8)
1. the preparation method of a CNT hollow-fibre membrane is characterized in that, may further comprise the steps:
(1) acidifying of CNT: CNT is placed in the mixed liquor of red fuming nitric acid (RFNA) and the concentrated sulfuric acid, 40~80 ℃ of lower insulations 2~6 hours; Then mixed liquor is diluted, and carbon nanotube separation out;
(2) electrophoretic deposition: the carbon nanotube dispersed after the acidifying in saturated monohydroxy alcohol, and is added the magnesium nitrate of 20~200mg/L; Then, this carbon nano tube dispersion liquid is poured in the electrodeposit reaction device; Wire is as masterplate, and as the negative electrode of electrophoresis system; Voltage is set as 30~160V, and the electrophoretic deposition time is made as 1~10 minute, but successive sedimentation repeatedly;
(3) anaerobic calcining: after deposition process was finished, the wire that the surface is covered with carbon nanotube layer was calcined under 200~1000oC 0.5~4 hour at oxygen free condition, naturally cooled to room temperature;
(4) remove template: the wire that is covered with carbon nanotube layer after will calcining is put into FeCl
3In/HCl the etching liquid, the wire that melts away namely obtains the hollow-fibre membrane that the full CNT of independent self-supporting forms.
2. preparation method according to claim 1 is characterized in that, described in the step (1) in the nitration mixture volume ratio of red fuming nitric acid (RFNA) and the concentrated sulfuric acid be 1:0~5; The separation method of CNT is vacuum filtration or high speed centrifugation described in the step (1).
3. preparation method according to claim 1 and 2 is characterized in that, saturated monohydroxy alcohol is absolute ethyl alcohol, anhydrous isopropyl alcohol or anhydrous normal butyl alcohol described in the step (2); Described in the step (2) in the carbon nano tube dispersion liquid content of CNT be 100~500mg/L; Wire described in the step (2) is iron wire, copper wire, aluminium wire, titanium silk or nickel wire; Frequency of depositing is 1~20 time described in the step (2).
4. preparation method according to claim 1 and 2 is characterized in that, oxygen free condition is vacuum or inert gas shielding described in the step (3).
5. preparation method according to claim 3 is characterized in that, oxygen free condition is vacuum or inert gas shielding described in the step (3).
6. according to claim 1,2 or 5 described preparation methods, it is characterized in that, the etching liquid composition consists of 0.5~5mol/L FeCl described in the step (4)
3/ 0.1~1mol/L HCl.
7. preparation method according to claim 3 is characterized in that, the etching liquid composition consists of 0.5~5mol/L FeCl described in the step (4)
3/ 0.1~1mol/L HCl.
8. preparation method according to claim 4 is characterized in that, the etching liquid composition consists of 0.5~5mol/L FeCl described in the step (4)
3/ 0.1~1mol/L HCl.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310272800.4A CN103316594B (en) | 2013-07-01 | 2013-07-01 | Preparation method of carbon-nanotube hollow fiber membranes |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310272800.4A CN103316594B (en) | 2013-07-01 | 2013-07-01 | Preparation method of carbon-nanotube hollow fiber membranes |
Publications (2)
Publication Number | Publication Date |
---|---|
CN103316594A true CN103316594A (en) | 2013-09-25 |
CN103316594B CN103316594B (en) | 2014-11-12 |
Family
ID=49185808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310272800.4A Active CN103316594B (en) | 2013-07-01 | 2013-07-01 | Preparation method of carbon-nanotube hollow fiber membranes |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN103316594B (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104174299A (en) * | 2014-07-30 | 2014-12-03 | 中国海洋大学 | High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof |
WO2015131436A1 (en) * | 2014-03-05 | 2015-09-11 | 大连理工大学 | Method for preparing carbon nanotube hollow fiber membrane on large scale |
CN106298268A (en) * | 2016-09-12 | 2017-01-04 | 东华大学 | Graphene/ conductive polymer hydridization doughnut and preparation method and application |
CN106400077A (en) * | 2016-09-12 | 2017-02-15 | 东华大学 | Graphene hollow fiber and continuous preparation method thereof |
CN106637511A (en) * | 2016-09-12 | 2017-05-10 | 东华大学 | Graphene porous fiber and continuous preparation method thereof |
CN107460725A (en) * | 2017-07-13 | 2017-12-12 | 东华大学 | A kind of phosphatization cobalt carbon nano-fiber composite material of sulfur doping and preparation method thereof |
CN109022495A (en) * | 2018-09-11 | 2018-12-18 | 华东理工大学 | A kind of method of micro-reduction carbon dioxide methane phase |
CN110273136A (en) * | 2019-06-24 | 2019-09-24 | 大连理工大学 | A kind of self-supporting hollow carbon tunica fibrosa and preparation method thereof and the application in lithium-sulfur cell |
CN110327789A (en) * | 2019-07-05 | 2019-10-15 | 大连理工大学 | A kind of carbon nanotube/nano fiber conductive composite film and preparation method thereof |
CN111298664A (en) * | 2020-03-16 | 2020-06-19 | 中国人民解放***箭军工程设计研究院 | Hollow fiber gas separation composite membrane and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101306351A (en) * | 2008-07-09 | 2008-11-19 | 厦门大学 | Solid phase micro-extraction extraction head using odd-tube carbon nano-tube as coating and its preparation method |
CN102560415A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院上海硅酸盐研究所 | Three-dimensional graphene/metal line or metal wire composite structure and preparation method thereof |
SE1130061A1 (en) * | 2011-06-15 | 2012-12-16 | Sht Smart High Tech Ab | Template-based manufacture of covalently bonded three-dimensional networks of large hollow carbon nanotubes |
-
2013
- 2013-07-01 CN CN201310272800.4A patent/CN103316594B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101306351A (en) * | 2008-07-09 | 2008-11-19 | 厦门大学 | Solid phase micro-extraction extraction head using odd-tube carbon nano-tube as coating and its preparation method |
SE1130061A1 (en) * | 2011-06-15 | 2012-12-16 | Sht Smart High Tech Ab | Template-based manufacture of covalently bonded three-dimensional networks of large hollow carbon nanotubes |
CN102560415A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院上海硅酸盐研究所 | Three-dimensional graphene/metal line or metal wire composite structure and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
GUOWEN MENG ET AL.: "A General Synthetic Approach to Interconnected Nanowire/Nanotube and Nanotube/Nanowire/Nanotube Heterojunctions with Branched Topology", 《ANGEWANDTE CHEMIE》, 31 December 2009 (2009-12-31), pages 7302 - 7306 * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015131436A1 (en) * | 2014-03-05 | 2015-09-11 | 大连理工大学 | Method for preparing carbon nanotube hollow fiber membrane on large scale |
US10179314B2 (en) | 2014-03-05 | 2019-01-15 | Dalian University Of Technology | Method for the high-throughput preparation of carbon nanotube hollow fiber membranes |
CN104174299B (en) * | 2014-07-30 | 2017-06-23 | 中国海洋大学 | High flux forward osmosis membrane based on ultra-thin supporting layer and preparation method thereof |
CN104174299A (en) * | 2014-07-30 | 2014-12-03 | 中国海洋大学 | High-flux positive osmosis membrane based on ultrathin support layer and preparation method thereof |
CN106298268A (en) * | 2016-09-12 | 2017-01-04 | 东华大学 | Graphene/ conductive polymer hydridization doughnut and preparation method and application |
CN106400077A (en) * | 2016-09-12 | 2017-02-15 | 东华大学 | Graphene hollow fiber and continuous preparation method thereof |
CN106637511A (en) * | 2016-09-12 | 2017-05-10 | 东华大学 | Graphene porous fiber and continuous preparation method thereof |
CN106298268B (en) * | 2016-09-12 | 2018-10-26 | 东华大学 | Graphene/ conductive polymer hydridization doughnut and the preparation method and application thereof |
CN106637511B (en) * | 2016-09-12 | 2019-01-22 | 东华大学 | A kind of graphene porous fibre and its continuous preparation method |
CN107460725B (en) * | 2017-07-13 | 2020-05-05 | 东华大学 | Sulfur-doped cobalt phosphide-carbon nanofiber composite material and preparation method thereof |
CN107460725A (en) * | 2017-07-13 | 2017-12-12 | 东华大学 | A kind of phosphatization cobalt carbon nano-fiber composite material of sulfur doping and preparation method thereof |
CN109022495A (en) * | 2018-09-11 | 2018-12-18 | 华东理工大学 | A kind of method of micro-reduction carbon dioxide methane phase |
CN109022495B (en) * | 2018-09-11 | 2022-03-29 | 华东理工大学 | Method for producing methane by reducing carbon dioxide with microorganisms |
CN110273136A (en) * | 2019-06-24 | 2019-09-24 | 大连理工大学 | A kind of self-supporting hollow carbon tunica fibrosa and preparation method thereof and the application in lithium-sulfur cell |
CN110273136B (en) * | 2019-06-24 | 2021-07-09 | 大连理工大学 | Self-supporting hollow carbon fiber membrane, preparation method thereof and application thereof in lithium-sulfur battery |
CN110327789A (en) * | 2019-07-05 | 2019-10-15 | 大连理工大学 | A kind of carbon nanotube/nano fiber conductive composite film and preparation method thereof |
CN110327789B (en) * | 2019-07-05 | 2022-02-15 | 大连理工大学 | Carbon nano tube/nano fiber conductive composite film and preparation method thereof |
CN111298664A (en) * | 2020-03-16 | 2020-06-19 | 中国人民解放***箭军工程设计研究院 | Hollow fiber gas separation composite membrane and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN103316594B (en) | 2014-11-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103316594B (en) | Preparation method of carbon-nanotube hollow fiber membranes | |
CN108251076B (en) | Carbon nanotube-graphene composite heat dissipation film, and preparation method and application thereof | |
Ji et al. | Advanced Graphene‐Based Binder‐Free Electrodes for High‐Performance Energy Storage | |
CN103058172B (en) | Preparation method of carbon nanometer tube-graphene composite material | |
CN107425180B (en) | Three-dimensional graphene/silicon composite system, preparation method and application thereof | |
Wang et al. | Recent progress of flexible sulfur cathode based on carbon host for lithium-sulfur batteries | |
CN108258210B (en) | Preparation method of 3D porous graphene/carbon nanotube-nano silicon aerogel lithium ion battery cathode material | |
CN104028112B (en) | The method of Carbon-nanotube hollow fiber membrane is prepared in a kind of scale | |
WO2016173111A1 (en) | Graphene dispersing agent and preparation method therefor | |
Kong et al. | Facile synthesis of CuO hollow nanospheres assembled by nanoparticles and their electrochemical performance | |
CN108039465B (en) | Composite electrode material, preparation method and application thereof | |
Wang et al. | Recent progress in flexible energy storage materials for lithium-ion batteries and electrochemical capacitors: A review | |
CN102153076A (en) | Method for preparing graphene with high crystallinity | |
CN103613093B (en) | A kind of hydrogen reducing prepares the method for Graphene | |
CN110970620A (en) | Preparation method of high-stability graphene/carbon nanotube composite conductive slurry | |
CN104157840A (en) | Preparation method of graphene coated silica nanotube composite negative electrode material for lithium ion battery | |
Ma et al. | Scallion-inspired graphene scaffold enabled high rate lithium metal battery | |
Yeon et al. | A new era of integrative ice frozen assembly into multiscale architecturing of energy materials | |
CN111554915A (en) | 3D printing ink, preparation method thereof and electrode printed by 3D printing ink | |
CN113223776A (en) | Self-supporting MXene/MWCNT flexible composite film and preparation method and application thereof | |
Wu et al. | Direct fabrication of carbon nanotube-graphene hybrid films by a blown bubble method | |
CN109713302A (en) | Under a kind of ultralow temperature can big multiplying power charge and discharge lithium ion battery and preparation method thereof | |
WO2017018556A1 (en) | Metal-carbon nanofiber and production method thereof | |
Lu et al. | 3D carbiyne nanospheres boosting excellent lithium and sodium storage performance | |
CN109786196B (en) | Method for preparing grid of transmission electron microscope |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |