CN103342351B - Method and device for preparing directionally arranged bucky paper in large scale - Google Patents
Method and device for preparing directionally arranged bucky paper in large scale Download PDFInfo
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- CN103342351B CN103342351B CN201310287156.8A CN201310287156A CN103342351B CN 103342351 B CN103342351 B CN 103342351B CN 201310287156 A CN201310287156 A CN 201310287156A CN 103342351 B CN103342351 B CN 103342351B
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002002 slurry Substances 0.000 claims abstract description 39
- 238000005345 coagulation Methods 0.000 claims abstract description 36
- 230000015271 coagulation Effects 0.000 claims abstract description 34
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 29
- 238000007493 shaping process Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 7
- 229940037003 alum Drugs 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 210000000481 breast Anatomy 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000835 fiber Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012982 microporous membrane Substances 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- -1 then Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
The invention discloses a method and a device for preparing directionally arranged bucky paper in large scale. The method comprises the following steps of dispersing, positioning the ejection, filtering, drying, shaping, drying and peeling off, wherein the step of positioning the ejection includes distributing carbon nano tubes or a carbon nano fiber dispersing liquid in a coagulation liquid flowing at a directionally high speed, and the carbon nano tubes or carbon nano fibers are subjected to a fluid shearing force, are directionally arranged towards the flowing direction, and are coagulated and fixed by the coagulation liquid. The device comprises a bi-path directional slurry flowing and distributing device and a filtering, shaping and drying device, wherein the bi-path directional slurry flowing and distributing device is used for distributing the slurry in one path of the carbon nano tubes or the carbon nano fiber dispersing liquid; the coagulation liquid is distributed in another path; the carbon nano tubes or the carbon nano fiber dispersing liquid is distributed on the coagulation liquid; the flow velocity of the coagulation liquid is greater than the flow velocity of the slurry. The method for preparing the directionally arranged bucky paper in large scale is low in cost and can conveniently realize large-scale production, and meanwhile the device for preparing the directionally arranged bucky paper in large scale can be easily transformed from the conventional paper making machine, so that the device is convenient to popularize.
Description
Technical field
The present invention relates to a kind of carbon nano based material preparation method and device, particularly the method and apparatus of Buckie paper that aligns of a kind of extensive preparation.
Background technology
Carbon nanotube and carbon nanofiber belong to one-dimensional carbon nano material, have the characteristics such as excellent mechanics, electricity, unique chemically reactive and high-specific surface area.Fuel cell electrode, catalytic carrier, electrode of super capacitor, lithium ion cell electrode, electromagnetic shielding and absorbing material can be widely used in, high shock material, carbon nanometer strengthen composite plastic, artificial-muscle base material, have broad application prospects.But the carbon nanotube of macrostate and carbon nanofiber are Powdered, directly apply inconvenience in many aspects, the base material of macroscopic view must be made into, not lose the performance of its nano material simultaneously, just can be convenient to application.
Buckie paper is the paper-like material being gathered into macroscopic view by a kind of or mixing in Single Walled Carbon Nanotube, double-walled carbon nano-tube, multi-walled carbon nano-tubes and carbon nanofiber in non-woven fabrics form.It had both remained the characteristic of carbon nanomaterial, possessed again the operability of macroscopic material.
The performance of the Buckie paper in nonwoven cloth-like of this direct preparation, although retain the characteristic of single-root carbon nano-tube and carbon nanofiber in specific surface and chemically reactive, in conduction, heat conduction and mechanical strength, but can not show a candle to single carbon nanotube and carbon nanofiber.So just restriction Buckie paper practical application in some respects.
If each the root carbon nanotube in Buckie paper and carbon nanofiber can be made all to align towards a direction, so the conduction of Buckie paper, heat conduction and mechanical strength will significantly strengthen.For preparing the Buckie paper aligned, existing many scientists are in effort at present.The researchist of Univ Pennsylvania USA and Rice University and professor Wang Ben of Florida State University organize the ultrastrong magnetic field all reporting on open magazine and Buckie paper shaping for suction filtration is placed in several tesla, thus have obtained the Buckie paper aligned.The researchist of U.S.'s Brigham Young University also reports a kind of method preparing orientational alignment carbon nano-tube at open magazine Nano Lett.: be on the silicon chip of 20 degree at inclination angle by the carbon nanotube liquid of 20 microlitres, then silica tube is placed in, logical as flow velocity be the argon gas stream 10 minutes of 6-9cm/s, the carbon nano-array that oven dry both must align.Recently, a kind of method that the researchist in Foxconn of Tsing-Hua University nanosecond science and technology research centre have employed novelty prepares the Buckie paper aligned: first adopt chemical vapour deposition at grown above silicon one deck carbon nano pipe array arranged vertically, then at upper cover one deck microporous membrane, then, microporous membrane is rolled from a direction with a cylindrical roller, carbon nano pipe array is toppled over towards a direction just as domino, the carbon nano pipe array of then toppling over together is torn together with microporous membrane, finally, drip a little ethanol on microporous membrane, carbon nano pipe array is torn it down from microporous membrane, just become the Buckie paper aligned.
But, prepare the method for the Buckie paper aligned above, be no matter adopt ultrastrong magnetic field, air-flow blows method, or drum process, be all difficult to realize extensive preparation, also or manufacturing cost too high, be difficult to be generalized in industrial production.
Here the phenomenon in a kind of modern paper is first inserted, so that for the invention provides place mat.In paper pulp, vegetable fibre arrangement after making beating is rambling, but on the paper machine run up during copy paper, fiber can due to the effect of center of gravity and inertia, most fiber can align along the copper mesh direction of motion of paper machine, just as the wood in water is along the water (flow) direction arrangement.Although due to the oscillating action of paper machine, make a small amount of fibre array still become mixed and disorderly, the directivity of fibre array is weakened to some extent, and the fiber generally in paper still presents the difference of obvious vertical and horizontal, and Here it is defines the silk tuft of paper.The silk tuft of paper is usually considered to harmful in paper printing.The present invention based on paper silk tuft formation basic theory, will prepare the Buckie paper aligned.
Summary of the invention
The first object of the present invention is a kind of Buckie paper method providing preparation being applicable to heavy industrialization to align; Second object is the device providing real preceding method.
The first object of the present invention is achieved in that dispersion process, sprays orientation process, is filtered dry type-approval process, dries and peels off; Described injection orientation process is for starch in being in directed swiftly flowing coagulation liquid by carbon nanotube or carbon nanofiber dispersion liquid cloth, and carbon nanotube or carbon nanofiber, by hydrodynamic shear effect, align towards flow direction, and fixing by coagulation liquid cohesion.
Described coagulation liquid is the one in alum liquor, alum solution, ferrum sulfuricum oxydatum solutum, polyvinyl alcohol solution, polyacrylamide solution.
Describedly being filtered dry sizing part, for being fallen on displacement filter screen by the slurries of preliminary directional at-tachment, being filtered dry fast simultaneously in further orientation; Described filter screen travel direction and coagulation liquid flow direction acutangulate.
Described dispersion process, adopts carbon nanotube or carbon nanofiber hydrophilic functional groups to modify and the mode adding tensio-active agent and be combined.
The second object of the present invention is achieved in that and comprises two-way oriented flow slurry mortar distributor and filtering shaping drying unit; Described two-way oriented flow slurry mortar distributor, for carbon nanotube or carbon nanofiber dispersion slurries are from a road cloth slurry, coagulation liquid is from another road cloth slurry, and carbon nanotube or carbon nanofiber dispersion slurries are distributed on coagulation liquid, and coagulation liquid velocity ratio slurry flow rate is large.
Described filtering shaping drying unit, adopts modern common fourdrinier machine structure.
Described two-way oriented flow slurry mortar distributor, comprises dispersion slurries locker room, flow valve, dispersion slurries pulp distributor, coagulation liquid pulp distributor, liquid absorbing pump, coagulation liquid storage barrel.
Described filtering shaping drying unit, comprises water suction breast roll, suction flat box, felt wrapped roll, vacuum dehydration roller, filtering shaping net, dries couch roll, drives net roller, cleaning roller, rinser, filter screen rectifier.
With prepare at present compared with directed Buckie paper method, the method for the Buckie paper that a kind of extensive preparation in the present invention aligns, has with low cost, is convenient to realize large-scale production; The device of the Buckie paper that the preparation in the present invention simultaneously aligns easily is come from existing paper machine transformation, is convenient to promote.
Accompanying drawing explanation
Fig. 1 sprays orientation process in the present invention, is filtered dry type-approval process principle schematic;
In figure: carbon nanotube or Fiber Distribution schematic diagram in 1-dispersion liquid, 2-sprays orientation process, and 3-sprays carbon nanotube or Fiber Distribution schematic diagram after orientation process, and 4-is filtered dry type-approval process, and 5-is filtered dry carbon nanotube or Fiber Distribution schematic diagram after type-approval process.
Fig. 2 is the structural representation preparing the Buckie paper apparatus aligned in the present invention on a large scale.
In figure: 1-disperses slurries locker room, 2-flow valve, 3-to disperse slurries pulp distributor, 4-coagulation liquid pulp distributor, 5-liquid absorbing pump, 6-coagulation liquid storage barrel, 7-water suction breast roll, 8-suction flat box, 9-felt wrapped roll, 10-vacuum dehydration roller, 11-filtering shaping net, 12-oven dry couch roll, 13-to drive net roller, 14-cleaning roller, 15-rinser, 16-filter screen rectifier.
Fig. 3 is the SEM photo of the Buckie paper aligned prepared in the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further illustrated, but limited the present invention never in any form, and according to the teachings of the present invention done any change or replacement, all belong to protection scope of the present invention.
As shown in Figure 1, the inventive method comprises dispersion process in reference, sprays orientation process 2, is filtered dry type-approval process 4, dries and peels off; Described injection orientation process is for starch in being in directed swiftly flowing coagulation liquid by carbon nanotube or carbon nanofiber dispersion liquid cloth, carbon nanotube or carbon nanofiber are by hydrodynamic shear effect, align towards flow direction, and it is fixing by coagulation liquid cohesion, and it is fixing by coagulation liquid cohesion, define the cluster of many inner orientations arrangement, and the vibration owing to splashing down between cluster and cluster, arrangement directional property is upset 3; Cluster be formed with the filter screen being beneficial to and selecting mesh larger, accelerate suction filtration speed, simultaneously cluster inertia compared with carbon nanotube and carbon nanofiber large; The cluster of inner orientation arrangement enters and is filtered dry type-approval process 4, and owing to being subject to the displacement effect of filter screen, align reinforcement between cluster, meanwhile, rete is filtered dry fast, thus the state that aligns is fixed.
Described coagulation liquid is the one in alum liquor, alum solution, ferrum sulfuricum oxydatum solutum, polyvinyl alcohol solution, polyacrylamide solution.
Describedly being filtered dry sizing part, for being fallen on displacement filter screen by the slurries of preliminary directional at-tachment, being filtered dry fast simultaneously in further orientation; Described filter screen travel direction and coagulation liquid flow direction acutangulate.
Described dispersion process, adopts carbon nanotube or carbon nanofiber hydrophilic functional groups to modify and the mode adding tensio-active agent and be combined.
Below in conjunction with Fig. 1, explain further and spray orientation process 2, be filtered dry type-approval process 4.As shown in Figure 1, carbon nanotube or fiber, after dispersion, are to be distributed in liquid 1 in a jumble; Through spraying orientation process 2, carbon nanotube or carbon nanofiber dispersion liquid cloth are starched in being in directed swiftly flowing coagulation liquid, and carbon nanotube or carbon nanofiber, by hydrodynamic shear effect, align towards flow direction,
Apparatus of the present invention comprise two-way oriented flow slurry mortar distributor and filtering shaping drying unit; Described two-way oriented flow slurry mortar distributor, for carbon nanotube or carbon nanofiber dispersion slurries are from a road cloth slurry, coagulation liquid is from another road cloth slurry, and carbon nanotube or carbon nanofiber dispersion slurries are distributed on coagulation liquid, and coagulation liquid velocity ratio slurry flow rate is large.
Described filtering shaping drying unit, adopts modern common fourdrinier machine structure.
As shown in Figure 2, described two-way oriented flow slurry mortar distributor, comprises dispersion slurries locker room 1, flow valve 2, dispersion slurries pulp distributor 3, coagulation liquid pulp distributor 4, liquid absorbing pump 5, coagulation liquid storage barrel 6.
As shown in Figure 2, described filtering shaping drying unit, comprises water suction breast roll 7, suction flat box 8, felt wrapped roll 9, vacuum dehydration roller 10, filtering shaping net 11, dries couch roll 12, drives net roller 13, cleaning roller 14, rinser 15, filter screen rectifier 16.
Fig. 3 is the SEM photo of the Buckie paper aligned prepared in the present invention, most of carbon nanofiber and have orientation towards direction shown in arrow from picture.
Claims (7)
1. prepare a method for the Buckie paper aligned on a large scale, it is characterized in that, comprise dispersion process, spray orientation process, be filtered dry type-approval process, dry and peel off; Described injection orientation process is for starch in being in directed swiftly flowing coagulation liquid by carbon nanotube or carbon nanofiber dispersion liquid cloth, and carbon nanotube or carbon nanofiber, by hydrodynamic shear effect, align towards flow direction, and fixing by coagulation liquid cohesion; Describedly being filtered dry type-approval process, for being fallen on displacement filter screen by the slurries of preliminary directional at-tachment, being filtered dry simultaneously directed further more fast; Described filter screen travel direction and coagulation liquid flow direction acutangulate.
2. the method for the Buckie paper aligned according to a kind of extensive preparation described in claim 1, it is characterized in that, described coagulation liquid is the one in alum liquor, alum solution, ferrum sulfuricum oxydatum solutum, polyvinyl alcohol solution, polyacrylamide solution.
3. the method for the Buckie paper aligned according to a kind of extensive preparation described in claim 1, is characterized in that, described dispersion process, adopts carbon nanotube or carbon nanofiber hydrophilic functional groups to modify and the mode adding tensio-active agent and be combined.
4. prepare a device for the Buckie paper aligned on a large scale, it is characterized in that, comprise two-way oriented flow slurry mortar distributor and filtering shaping drying unit; Described two-way oriented flow slurry mortar distributor, for carbon nanotube or carbon nanofiber dispersion slurries are from a road cloth slurry, coagulation liquid is from another road cloth slurry, and carbon nanotube or carbon nanofiber dispersion slurries are distributed on coagulation liquid, and coagulation liquid velocity ratio slurry flow rate is large.
5. the device of Buckie paper that aligns of a kind of extensive preparation according to claim 4, is characterized in that, described filtering shaping drying unit, adopts modern common fourdrinier machine structure.
6. the device of Buckie paper that aligns of a kind of extensive preparation according to claim 4, it is characterized in that, described two-way oriented flow slurry mortar distributor, comprises dispersion slurries locker room, flow valve, dispersion slurries pulp distributor, coagulation liquid pulp distributor, liquid absorbing pump, coagulation liquid storage barrel.
7. the device of the Buckie paper aligned according to a kind of extensive preparation described in claim 4, it is characterized in that, described filtering shaping drying unit, comprises water suction breast roll, suction flat box, felt wrapped roll, vacuum dehydration roller, filtering shaping net, dries couch roll, drives net roller, cleaning roller, rinser, filter screen rectifier.
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| CN201310287156.8A CN103342351B (en) | 2013-07-10 | 2013-07-10 | Method and device for preparing directionally arranged bucky paper in large scale |
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| CN201310287156.8A CN103342351B (en) | 2013-07-10 | 2013-07-10 | Method and device for preparing directionally arranged bucky paper in large scale |
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| CN103342351B true CN103342351B (en) | 2015-02-18 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9713820B2 (en) | 2014-06-02 | 2017-07-25 | The Boeing Company | System and method of forming a nanotube mesh structure |
| CN105948024B (en) * | 2016-04-29 | 2018-01-09 | 清华大学 | The preparation method of macroscopical aggregation of micro Nano material |
| US10873026B2 (en) * | 2017-03-10 | 2020-12-22 | Wisconsin Alumni Research Foundation | Alignment of carbon nanotubes in confined channels |
| CN117536011B (en) * | 2023-11-13 | 2024-09-13 | 浙江星辉新材料科技有限公司 | Control method for directional arrangement of carbon filaments of wet-process felt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180460A (en) * | 2011-03-17 | 2011-09-14 | 东华大学 | Preparation method of highly-oriented carbon nanotube paper |
| CN102659092A (en) * | 2012-04-12 | 2012-09-12 | 东华大学 | Simple controllable carbon nanotube paper preparation device and method |
| CN102877367A (en) * | 2012-10-26 | 2013-01-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube/short-fiber composited nano-carbon paper and continuous preparation method thereof |
| CN103015256A (en) * | 2012-12-11 | 2013-04-03 | 肖辉 | Carbon nanofiber paper and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7875219B2 (en) * | 2007-10-04 | 2011-01-25 | Nanotek Instruments, Inc. | Process for producing nano-scaled graphene platelet nanocomposite electrodes for supercapacitors |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180460A (en) * | 2011-03-17 | 2011-09-14 | 东华大学 | Preparation method of highly-oriented carbon nanotube paper |
| CN102659092A (en) * | 2012-04-12 | 2012-09-12 | 东华大学 | Simple controllable carbon nanotube paper preparation device and method |
| CN102877367A (en) * | 2012-10-26 | 2013-01-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | Carbon nanotube/short-fiber composited nano-carbon paper and continuous preparation method thereof |
| CN103015256A (en) * | 2012-12-11 | 2013-04-03 | 肖辉 | Carbon nanofiber paper and preparation method thereof |
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