CN106396680A - Preparation method of flexible ultrathin carbon nanotube paper - Google Patents

Preparation method of flexible ultrathin carbon nanotube paper Download PDF

Info

Publication number
CN106396680A
CN106396680A CN201610806868.XA CN201610806868A CN106396680A CN 106396680 A CN106396680 A CN 106396680A CN 201610806868 A CN201610806868 A CN 201610806868A CN 106396680 A CN106396680 A CN 106396680A
Authority
CN
China
Prior art keywords
carbon nanotube
nanotube paper
paper
cnt
warming
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.)
Pending
Application number
CN201610806868.XA
Other languages
Chinese (zh)
Inventor
孙晓刚
邱志文
庞志鹏
蔡满园
陈珑
刘珍红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanchang University
Original Assignee
Nanchang University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nanchang University filed Critical Nanchang University
Priority to CN201610806868.XA priority Critical patent/CN106396680A/en
Publication of CN106396680A publication Critical patent/CN106396680A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/522Graphite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/62218Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5208Fibers
    • C04B2235/5252Fibers having a specific pre-form
    • C04B2235/5256Two-dimensional, e.g. woven structures
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52Constituents or additives characterised by their shapes
    • C04B2235/5284Hollow fibers, e.g. nanotubes
    • C04B2235/5288Carbon nanotubes
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658Atmosphere during thermal treatment
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/661Multi-step sintering
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74Physical characteristics
    • C04B2235/77Density

Abstract

The invention provides a preparation method of flexible ultrathin carbon nanotube paper. The preparation method comprises steps as follows: firstly, carbon nanotubes wetted with ethanol or acetone are added to distilled water and subjected to ultrasonic dispersion; then, pulp fibers are added, a high-speed shearing emulsifying machine is used for sufficient mixing and dispersion, and conductive carbon nanotube paper is prepared with an ordinary papermaking process; the carbon nanotube paper is modified and then subjected to graphitization; finally, the carbon nanotube paper is rolled by a roll crusher. Compared with conventional carbon nanotube paper, the carbon nanotube paper has the advantages that the conductivity is improved remarkably, and the strength and the flexibility are improved apparently through rolling. A product can be cut into required shapes and sizes, or a conductive carbon nanotube paper product with the specific shape and size is directly manufactured.

Description

A kind of preparation method of flexible ultra-thin carbon nanotube paper
Technical field
The invention belongs to chemistry and field of functional materials, be related to the pretreatment of CNT, dispersion, charing, graphitization and The technology such as rolling.
Background technology
CNT has excellent electrical conduction, heat-conductive characteristic, so that CNT is widely used in many fields Space, particularly outstanding mechanical property and mechanical performance, because CNT is nano material, its excellent physical and chemical performance It is difficult to macroscopically showing.So in a lot of research, paper being relied on to carry CNT as matrix and to obtain a kind of being combined The conductive paper with superperformance.
The preparation method of the carbon nano tube conductive paper of report is broadly divided into two kinds at present:The first, by preparing carbon nanometer Pipe conductive ink is coated on paper, and this method can retain the physical properties such as the form of good paper, intensity, but this conductive paper is Single-sided conductive, it is hardly formed the conductive network of three-dimensional;Second, will be black by carbon nanotube conducting by the method for papermaking again Again it is combined into paper, this method can utilize the adsorptivity of paper and easy formability, so that CNT is filled after being combined with paper fiber Point dispersion, be adsorbed in paper fiber surface, form three-dimensional conductive network, but the carbon nanotube paper that obtains of this method lose original The intensity of paper and physical property, limit the space of its application.
Charing, graphitization are the conventional means in heat treatment, are applied to make the carbon content rate of material improve in material with carbon element, Make amorphous carbon farthest be converted into crystalline structure, improve electric conductivity and the thermal conductivity of material.Rolling process can make material Material internal structure consolidation, defect is less, and uniformity improves, and then improves intensity and the pliability of material.
Content of the invention
The purpose of the present invention is a kind of preparation method of flexible ultra-thin carbon nanotube paper, can simply, quick, efficient make Standby flexible ultra-thin carbon nanotube paper, and process the performance of modified carbon nano-tube by series of process, thus improving CNT The serviceability of paper.
The present invention is achieved by the following technical solutions, and concrete steps include as follows.
(1)To add in distilled water in CNT after ethanol or acetone wetting, 1-3h processed using ultrasonic disperse, Make CNT dispersed in a liquid.
(2)Using high-speed shearing emulsion machine, pre-dispersed CNT and paper pulp fiber are sufficiently mixed, disperse, answered Close suspension.
(3)Compound suspension deposition is obtained carbon nano tube conductive paper by the method using common papermaking, is placed in vacuum drying Case, 65 DEG C are dried 1-3h.
(4)The modification of carbon nanotube paper, the carbon nanotube paper after peeling off is placed in vacuum carbonized stove, with 10-15 DEG C/min is warming up to 600 DEG C, is incubated 20-120min, then is warming up to 800 DEG C -1400 DEG C with 2-5 DEG C/min, temperature retention time is 1- 10h, is cooled to room temperature and takes out after terminating.
(5)By step(4)Carbon nanotube paper after charing process is placed in graphitizing furnace again, with the intensification of 5-20 DEG C/min Speed is warming up to 2300 DEG C -3000 DEG C, uses argon gas, nitrogen etc. to keep non-oxide inert gas to protect during graphitization processing Shield, is incubated 2-36h, cools to room temperature with the furnace and takes out.
(6)Carbon nanotube paper after graphitization processing is rolled by twin rollers, twin rollers roll-in thickness is 0.05-1mm, Density 0.1 ~ 0.4g/cm that after roll-in, carbon nanotube paper is3, thickness is 0.1-1mm.
The carbon nanotube paper of the present invention is obviously improved than front electric conductivity, through rolling, its intensity, pliability is obtained bright Aobvious improvement.Product of the present invention can be cut into the shapes and sizes of needs, or the carbon being manufactured directly to specific shapes and sizes Nanotube conductive paper product.
Brief description
Accompanying drawing 1 is the carbon nano tube conductive paper SEM figure of invention.
Accompanying drawing 2 is the carbon nano tube conductive paper photo of the present invention.
Specific embodiment
The present invention will be described further by following examples.
The present embodiment selects crystal whisker-shaped carbon nanotube(ZL201210067937.1、ZL201210304345.7)As conduction Agent.
Embodiment 1.
1st, 1g CNT is added in 500ml distilled water, add appropriate dispersant, process 1 hour through ultrasonic disperse Make CNT dispersed in a liquid.
2nd, by above-mentioned carbon nano-tube solution and paper pulp stirring mixing, by high-speed shearing emulsion machine by CNT and paper pulp Full and uniform dispersion.
3rd, scattered CNT and pulp solution are passed through to copy to filter into paper, vacuum drying is prepared into CNT and leads Electric paper.
4th, carbon nanotube paper is placed in the carbide furnace being filled with argon gas protection, is warming up to 600 DEG C with 10/min, insulation 60min, then it is warming up to 1200 DEG C with 3 DEG C/min, it is incubated 5h, be cooled to room temperature after terminating and take out.
5th, the carbon nanotube paper after carbonization treatment is placed in graphitizing furnace, is passed through argon gas as protective gas, with 15 DEG C/ The programming rate of min is warming up to 2800 DEG C, and temperature retention time is 12h, and cooling after graphitization terminates is taken out.
6th, the carbon nanotube paper after graphitization processing is passed through twin rollers rolling process, density is about 0.22g/cm3, thickness For 0.1mm.
Embodiment 2.
1st, 1g CNT is added in 500ml absolute ethyl alcohol, add appropriate dispersant, process 1 through ultrasonic disperse little When make CNT dispersed in a liquid.
2nd, by above-mentioned carbon nano-tube solution and paper pulp stirring mixing, then with high-speed shearing emulsion machine by CNT and paper pulp Full and uniform dispersion.
3rd, scattered CNT and pulp solution are passed through to copy to filter into paper, vacuum drying is prepared into CNT and leads Electric paper.
4th, carbon nanotube paper is placed in the carbide furnace being filled with argon gas protection, is warming up to 600 DEG C with 12/min, insulation 50min, then it is warming up to 1400 DEG C with 4 DEG C/min, it is incubated 6h, be cooled to room temperature after terminating and take out.
5th, the carbon nanotube paper after carbonization treatment is placed in graphitizing furnace, is passed through argon gas as protective gas, with 15 DEG C/ The programming rate of min is warming up to 2900 DEG C, and temperature retention time is 18h, and cooling after graphitization terminates is taken out.
6th, the carbon nanotube paper after graphitization processing is passed through twin rollers rolling process, density is about 0.39g/cm3, thickness For 0.05mm.

Claims (1)

1. a kind of preparation method of flexible ultra-thin carbon nanotube paper, is characterized in that comprising the steps:
(1)To add in distilled water in the CNT after ethanol or acetone wetting, ultrasonic disperse processes 1-3h, makes carbon nanometer Pipe is dispersed in a liquid;
(2)Using high-speed shearing emulsion machine, pre-dispersed CNT and paper pulp fiber are sufficiently mixed, disperse, obtain compound outstanding Turbid liquid;
(3)Compound suspension deposition is obtained carbon nano tube conductive paper by the method using common papermaking, is placed in vacuum drying box, and 65 DEG C 1-3h is dried;
(4)Carbon nanotube paper after peeling off is placed in vacuum carbonized stove, is warming up to 600 DEG C with 10-15 DEG C/min, be incubated 20- 120min, then it is warming up to 800 DEG C -1400 DEG C with 2-5 DEG C/min, temperature retention time is 1-10h, is cooled to room temperature and takes out after terminating;
(5)By step(4)Carbon nanotube paper after charing process is placed in graphitizing furnace again, with the programming rate of 5-20 DEG C/min It is warming up to 2300 DEG C -3000 DEG C, use argon gas, nitrogen etc. to keep non-oxide inert gas shielding during graphitization processing, protect Warm 2-36h, cools to room temperature with the furnace and takes out;
(6)Carbon nanotube paper after graphitization processing is rolled by twin rollers, twin rollers roll-in thickness is 0.05-1mm, roll-in Density 0.1 ~ 0.4g/cm that carbon nanotube paper is afterwards3, thickness is 0.1-1mm.
CN201610806868.XA 2016-09-07 2016-09-07 Preparation method of flexible ultrathin carbon nanotube paper Pending CN106396680A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610806868.XA CN106396680A (en) 2016-09-07 2016-09-07 Preparation method of flexible ultrathin carbon nanotube paper

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610806868.XA CN106396680A (en) 2016-09-07 2016-09-07 Preparation method of flexible ultrathin carbon nanotube paper

Publications (1)

Publication Number Publication Date
CN106396680A true CN106396680A (en) 2017-02-15

Family

ID=57998608

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610806868.XA Pending CN106396680A (en) 2016-09-07 2016-09-07 Preparation method of flexible ultrathin carbon nanotube paper

Country Status (1)

Country Link
CN (1) CN106396680A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106835847A (en) * 2017-03-13 2017-06-13 南昌大学 A kind of preparation method of bio-compatibility carbon nanometer tube/hydroxyapatite extrusion coating paper
CN107012720A (en) * 2017-03-13 2017-08-04 南昌大学 A kind of conductive non-woven fabrics preparation method of bio-compatible
CN108385450A (en) * 2018-01-23 2018-08-10 柔电(武汉)科技有限公司 A kind of carbon nanotube paper and preparation method thereof
CN109167093A (en) * 2018-09-03 2019-01-08 江西克莱威纳米碳材料有限公司 A kind of hydroxylating whisker carbon nanotube paper and preparation method thereof and a kind of lithium-sulfur cell
CN109256564A (en) * 2018-09-10 2019-01-22 江西克莱威纳米碳材料有限公司 Carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium-sulfur cell

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102561109A (en) * 2011-12-20 2012-07-11 南昌大学 Method for preparing carbon nano tube conductive paper
CN104129779A (en) * 2014-06-27 2014-11-05 桂林浩新科技服务有限公司 Preparation method of graphene-containing nano paper
CN105047940A (en) * 2015-06-16 2015-11-11 南昌大学 Preparation method of carbon nanotube film
CN105514434A (en) * 2016-01-19 2016-04-20 南昌大学 Preparation method of whisker-shaped carbon nano tube film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102561109A (en) * 2011-12-20 2012-07-11 南昌大学 Method for preparing carbon nano tube conductive paper
CN104129779A (en) * 2014-06-27 2014-11-05 桂林浩新科技服务有限公司 Preparation method of graphene-containing nano paper
CN105047940A (en) * 2015-06-16 2015-11-11 南昌大学 Preparation method of carbon nanotube film
CN105514434A (en) * 2016-01-19 2016-04-20 南昌大学 Preparation method of whisker-shaped carbon nano tube film

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
庞志鹏等: "碳纳米管导电纸的制备及改性研究", 《功能材料》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106835847A (en) * 2017-03-13 2017-06-13 南昌大学 A kind of preparation method of bio-compatibility carbon nanometer tube/hydroxyapatite extrusion coating paper
CN107012720A (en) * 2017-03-13 2017-08-04 南昌大学 A kind of conductive non-woven fabrics preparation method of bio-compatible
CN108385450A (en) * 2018-01-23 2018-08-10 柔电(武汉)科技有限公司 A kind of carbon nanotube paper and preparation method thereof
CN109167093A (en) * 2018-09-03 2019-01-08 江西克莱威纳米碳材料有限公司 A kind of hydroxylating whisker carbon nanotube paper and preparation method thereof and a kind of lithium-sulfur cell
CN109256564A (en) * 2018-09-10 2019-01-22 江西克莱威纳米碳材料有限公司 Carbon nanotube-graphite composite material, lithium sulfur battery anode material and lithium-sulfur cell
CN109256564B (en) * 2018-09-10 2021-07-09 江西克莱威纳米碳材料有限公司 Carbon nanotube-graphite composite material, lithium-sulfur battery positive electrode material and lithium-sulfur battery

Similar Documents

Publication Publication Date Title
CN106396680A (en) Preparation method of flexible ultrathin carbon nanotube paper
Fan et al. A lightweight and conductive MXene/graphene hybrid foam for superior electromagnetic interference shielding
CN106517171B (en) A kind of preparation method of graphene aerogel
CN104445153B (en) A kind of method being prepared charcoal nanometer roll by Graphene magnanimity
CN106633391B (en) A kind of abductive approach of polypropylene/glass fiber interface scorching structure
CN103613096B (en) Low-cost method for preparing graphene macroform
CN104108700B (en) A kind of grapheme material powder and preparation method
CN105802589A (en) High-strength heat-conducting film and preparation method thereof
CN109824033A (en) A kind of method of low cost preparation high thermal conductivity graphene film
CN110157931B (en) Nano carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof
CN107393622B (en) Graphene-titanium suboxide composite conductive agent and preparation method thereof
CN107055521A (en) The method and the graphene microballoon of prepare with scale height rule spherical graphite alkene microballoon
CN105752970B (en) A kind of preparation method of carbon nano tube/graphene compound
CN110028057A (en) A kind of graphene slurry and preparation method thereof with Investigation of stabilized dispersion of nano
Zhou et al. Fe3O4/carbonized cellulose micro-nano hybrid for high-performance microwave absorber
He et al. Construction of heterointerfaces and honeycomb-like structure for ultrabroad microwave absorption
Yue et al. Continuous growth of carbon nanotubes on the surface of carbon fibers for enhanced electromagnetic wave absorption properties
CN106206051A (en) A kind of Graphene modified activated carbon and application thereof
CN103818895B (en) A kind of preparation method of nitrogen atom doping graphene nano volume
CN103319820A (en) Preparation method of graphene and polymer conductive composite material
Toyoda et al. Intercalation of formic acid into carbon fibers and their exfoliation
CN110112384A (en) A kind of preparation method of porous graphene silicium cathode material
Pan et al. Enhanced thermal conductivity with ultralow filler loading via constructing branch-type heat transfer network
Chen et al. Two-step thermal treatment of electrochemical graphene oxide films for high-performance electrical heating and electromagnetic interference shielding
Huang et al. A highly flexible and conductive graphene-wrapped carbon nanofiber membrane for high-performance electrocatalytic applications

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170215

WD01 Invention patent application deemed withdrawn after publication