CN102677546B - Ionic liquid coated paper of thin-walled carbon nanotube and preparation method of ionic liquid coated paper - Google Patents

Ionic liquid coated paper of thin-walled carbon nanotube and preparation method of ionic liquid coated paper Download PDF

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CN102677546B
CN102677546B CN201210135002.2A CN201210135002A CN102677546B CN 102677546 B CN102677546 B CN 102677546B CN 201210135002 A CN201210135002 A CN 201210135002A CN 102677546 B CN102677546 B CN 102677546B
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ionic liquid
paper
carbon nano
tube
wall carbon
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CN102677546A (en
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骞伟中
郑超
余云涛
崔超婕
魏飞
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Tsinghua University
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Tsinghua University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The invention belongs to the technical field of conducting materials and discloses an ionic liquid coated paper of a thin-walled carbon nanotube and a preparation method of the ionic liquid coated paper. An ionic liquid in the paper of carbon nanotubes is evenly coated on the outer surfaces of the carbon nanotubes to form a coaxial structure, and then the carbon nanotubes are mutually lapped to form a net structure. The paper of the carbon nanotubes is prepared by the steps that firstly 15wt% to 30wt% of ionic liquid and the thin-walled carbon nanotube are subjected to dispersion mill, and then are compacted. The ionic liquid can have functions of dispersing the thin-walled carbon nanotube, opening tube bundles of the thin-walled carbon nanotube and serving as an adhesive. Compared with resistance of papers of thin-walled carbon nanotubes, which are directly compacted without using the ionic liquid, the resistance of the prepared paper of the thin-walled carbon nanotube is reduced by 20-40%, when the paper is used as an electrode material of a supercapacitor at a voltage of 4-6.5 volts, the performances of the supercapacitor are improved by 20-100%, and when the paper is used as a strength material, the tensile strength is improved by 20-100%. Besides, the preparation method has the advantages of being low in cost and easy to repeat and amplify.

Description

Paper of a kind of thin wall carbon nano-tube of ionic liquid parcel and preparation method thereof
Technical field
The invention belongs to conductive material technical field, particularly paper of a kind of thin wall carbon nano-tube of ionic liquid parcel and preparation method thereof.
Background technology
Thin wall carbon nano-tube is due to perfect structure, and chemical stability is high, and the characteristic such as specific area is large, conducts electricity very well, and draw ratio is large, recently by the electrode material as ultracapacitor gradually.Compared with the porous interior surface features of traditional active carbon electrode material, the surface of thin wall carbon nano-tube presents outer cage structure, is particularly suitable for the diffusion of electrolyte ion.This feature makes it be more applicable for organic electrolyte or the larger-size high voltage electric capacity of ion liquid type electrolyte plasma system.Such as, when thin wall carbon nano-tube is made to its mass fraction lower than 18% gel, thin wall carbon nano-tube is monodisperse status, and its outer surface utilization is abundant, and energy density is higher.But when for the field such as wind power generating set or heavy-duty machinery, generally all require ultracapacitor to there is higher volume energy density, will in minimum space, pile up electrode material as much as possible.Therefore,, by structure densification loose thin wall carbon nano-tube, become gradually the practical demand of its application.But because thin wall carbon nano-tube diameter is little, the model ylid bloom action power between pipe is very strong, and dense packing thin wall carbon nano-tube can cause its bunchy of attracting each other, thereby aperture is reduced, electrolyte ion diffusion difficulty, its surface area utilization ratio reduces, and capacitive property declines.In addition, thin wall carbon nano-tube density is little, in the time of direct compacting, is difficult for compacting and can makes a small amount of thin wall carbon nano-tube fly in air, has not only caused the loss of material, but also may contaminated environment or injury health.
Summary of the invention
The present invention is directed to above-mentioned thin wall carbon nano-tube in practical demand and the deficiencies in the prior art for ultracapacitor field, carried out the improvement of novelty, proposed paper of a kind of thin wall carbon nano-tube of ionic liquid parcel and preparation method thereof.
The invention provides a kind of paper of thin wall carbon nano-tube of ionic liquid parcel, it is characterized in that: the content of thin wall carbon nano-tube is 70wt%～85wt%, the content of ionic liquid is 15wt%～30wt%, wherein ionic liquid is evenly coated on the outer surface of thin wall carbon nano-tube, form coaxial structure, then thin wall carbon nano-tube overlaps mutually again, forms network structure.Described thin wall carbon nano-tube is one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube and three wall carbon nano tubes.
The preparation method who the invention still further relates to the paper of the thin wall carbon nano-tube of above-mentioned ionic liquid parcel, is characterized in that: the method concrete steps are as follows:
(1) thin wall carbon nano-tube is placed in to a container, add ionic liquid (the two fluoroform sulfimide salt of N-methyl butyl pyrrolidines of 20 DEG C～80 DEG C, the two fluoroform sulfimide salt of N-methyl butyl piperidines, the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole, 1-ethyl-3-methylimidazole tetrafluoroborate, the two fluoroform sulfimide salt of trimethyl the third ammonium, one or more in the two fluoroform sulfimide salt of dimethyl second QAE quaternary aminoethyl methyl ether and the two fluoroform sulfimide salt plasma liquid of 1-hexyl-3-methylimidazole), grind 1 hour～24 hours, make ionic liquid evenly be wrapped in the outer surface of thin wall carbon nano-tube.
(2) by above-mentioned gained mixture, carry out compacting, be prepared into a kind of paper of thin wall carbon nano-tube of ionic liquid parcel.
The present invention compared with prior art, has following beneficial effect:
1, the dielectricity of ionic liquid is strong, can overcome the Van der Waals force of thin wall carbon nano-tube interfascicular, and tube bank is diminished, and when for ultracapacitor field, can provide larger electrolyte/electrode material interface, thereby makes capacitive property improve 20%～100%.
2, use ionic liquid dispersing Nano carbon tubes, can make the CNT in unit are distribute more evenly, thereby when for strength materials, stressed more even.Viscosity of il is larger simultaneously, can play bonding agent, therefore, can make the TENSILE STRENGTH of the paper of CNT improve 20%～100%.
3, the viscosity of ionic liquid is larger, and there is to wetting action on thin wall carbon nano-tube surface, makes CNT be difficult for loss, and compacting process is simplified, and preparation cost declines.
4, ionic liquid aid dispersion is prepared the method for the paper of CNT, the highly purified thin wall carbon nano-tube that can use any preparation method to obtain, therefore be not subject to the restriction of the process of the method (as graphite acr method or chemical vapour deposition technique) of any direct this class formation of preparation, there is the characteristic that can amplify.
Detailed description of the invention
The invention provides paper of a kind of thin wall carbon nano-tube of ionic liquid parcel and preparation method thereof, below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1
After three wall carbon nano tubes of the double-walled carbon nano-tube of the Single Walled Carbon Nanotube of 1wt%, 80wt% and 19wt% are mixed, join the two fluoroform sulfimide salt ion liquid of N-methyl butyl pyrrolidines of 60 DEG C, wherein ionic liquid accounts for 15% of mixture gross mass.After grinding 24 hours, be that bulk density is 280kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 20% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; Be used for the electrode material of the ultracapacitor of working under 6.5V voltage time, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 35%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 45%.
Embodiment 2
By Single Walled Carbon Nanotube join 40 DEG C the two fluoroform sulfimide salt ion liquid of N-methyl butyl piperidines wherein ionic liquid account for 19% of mixture gross mass.After grinding 24 hours, be that bulk density is 320kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 40% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 5.5V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 45%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 100%.
Embodiment 3
By double-walled carbon nano-tube join 80 DEG C 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid wherein ionic liquid account for 25% of mixture gross mass.After grinding 2 hours, be that bulk density is 380kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 30% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 4V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 28%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 30%.
Embodiment 4
By three wall carbon nano tubes join 50 DEG C the two fluoroform sulfimide salt ion liquid of 1-ethyl-3-methylimidazole wherein ionic liquid account for 16% of mixture gross mass.After grinding 2 hours, be that bulk density is 350kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 28% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 4.5V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 20%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 20%.
Embodiment 5
After three wall carbon nano tubes of 50wt% are mixed with the double-walled carbon nano-tube of 50wt%, the mixed ionic liquid that joins the two fluoroform sulfimide salt of the 1-ethyl-3-methylimidazole tetrafluoroborate of 30 DEG C of 50wt% and the N-methyl butyl pyrrolidines of 50wt% wherein ionic liquid accounts for 18% of mixture gross mass.After grinding 10 hours, be that bulk density is 300kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 22% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 4.2V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 25%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 40%.
Embodiment 6
After the Single Walled Carbon Nanotube of 50wt% is mixed with the double-walled carbon nano-tube of 50wt%, join 30 DEG C the two fluoroform sulfimide salt ion liquid of dimethyl second QAE quaternary aminoethyl methyl ether wherein ionic liquid account for 23% of mixture gross mass.After grinding 12 hours, be that bulk density is 400kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 32% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 5V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 28%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 60%.
Embodiment 7
After the Single Walled Carbon Nanotube of 50wt% is mixed with three wall carbon nano tubes of 50wt%, join 80 DEG C the two fluoroform sulfimide salt ion liquid of trimethyl the third ammonium wherein ionic liquid account for 20% of mixture gross mass.After grinding 3 hours, be that bulk density is 400kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 35% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 5.5V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 30%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 50%.
Embodiment 8
After the double-walled carbon nano-tube of the Single Walled Carbon Nanotube of 9wt%, 80wt% is mixed with three wall carbon nano tubes of 11wt%, join 20 DEG C the two fluoroform sulfimide salt ion liquid of 1-ethyl-3-methylimidazole wherein ionic liquid account for 22% of mixture gross mass.After grinding 2 hours, be that bulk density is 400kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 27% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 4.2V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 23%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 80%.
Embodiment 9
After the double-walled carbon nano-tube of the Single Walled Carbon Nanotube of 80wt%, 9wt% is mixed with three wall carbon nano tubes of 11wt%, join 70 DEG C the two fluoroform sulfimide salt ion liquid of 1-hexyl-3-methylimidazole wherein ionic liquid account for 30% of mixture gross mass.After grinding 16 hours, be that bulk density is 200kg/m by its compacting 3paper.Directly the resistance of the paper of the CNT of compacting is low by 37% without ionic liquid parcel for the resistance ratio of the paper of above-mentioned CNT; While being used for the electrode material of the ultracapacitor of working under 6V voltage, than without ionic liquid parcel, directly capacitance and the energy density of the paper of the CNT of compacting are all high by 100%; During for strength materials, than without ionic liquid parcel, directly the TENSILE STRENGTH of the paper of the CNT of compacting is high by 20%.

Claims (3)

1. the paper of the thin wall carbon nano-tube of an ionic liquid parcel, it is characterized in that: the content of described thin wall carbon nano-tube is 70wt%～85wt%, the content of described ionic liquid is 15wt%～30wt%, wherein ionic liquid is evenly coated on the outer surface of thin wall carbon nano-tube, form coaxial structure, then thin wall carbon nano-tube overlaps mutually again, forms network structure;
Described ionic liquid is one or more in the two fluoroform sulfimide salt of N-methyl butyl pyrrolidines, the two fluoroform sulfimide salt of N-methyl butyl piperidines, the two fluoroform sulfimide salt of 1-ethyl-3-methylimidazole, 1-ethyl-3-methylimidazole tetrafluoroborate, the two fluoroform sulfimide salt of trimethyl the third ammonium, the two fluoroform sulfimide salt of dimethyl second QAE quaternary aminoethyl methyl ether and the two fluoroform sulfimide salt ion liquid of 1-hexyl-3-methylimidazole.
2. the paper of the thin wall carbon nano-tube of a kind of ionic liquid parcel according to claim 1, is characterized in that: described thin wall carbon nano-tube is one or more in Single Walled Carbon Nanotube, double-walled carbon nano-tube and three wall carbon nano tubes.
3. a preparation method for the paper of the thin wall carbon nano-tube of ionic liquid parcel claimed in claim 1, is characterized in that: the method concrete steps are as follows:
(1) thin wall carbon nano-tube is placed in to a container, adds the ionic liquid of 20 DEG C～80 DEG C, grind 1 hour～24 hours, make ionic liquid evenly be wrapped in the outer surface of thin wall carbon nano-tube;
(2) by above-mentioned gained mixture, carry out compacting, be prepared into a kind of paper of thin wall carbon nano-tube of ionic liquid parcel.
CN201210135002.2A 2012-05-02 2012-05-02 Ionic liquid coated paper of thin-walled carbon nanotube and preparation method of ionic liquid coated paper Active CN102677546B (en)

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CN103021676B (en) * 2012-12-18 2016-02-10 清华大学 A kind of electrolyte for high tension super capacitor and preparation method thereof
CN104841468B (en) * 2014-02-19 2017-05-03 中国科学院金属研究所 Carbon-based nonmetal solid alkali nanometer catalyst, and preparation method and application thereof
CN104479170A (en) * 2014-11-25 2015-04-01 上海交通大学 Method for preparing composite material through ionic liquid modified carbon nano tube
CN109111173B (en) * 2018-10-22 2020-10-30 宜昌力华新型建材有限公司 Pervious concrete and preparation method thereof
CN113797767B (en) * 2020-06-12 2022-10-28 四川大学 Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet

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CN1708454A (en) * 2002-10-23 2005-12-14 独立行政法人科学技术振兴机构 Composition in gel form comprising carbon nanotube and ionic liquid and method for production thereof

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