阅读说明：本技术 一种碳纳米管-离子液体-衍生纤维素复合膜和复合片的制备方法 (Preparation method of carbon nanotube-ionic liquid-derived cellulose composite membrane and composite sheet ) 是由 姚舜 陈琛 于 2020-06-12 设计创作，主要内容包括：本发明公开了一种碳纳米管-离子液体-衍生纤维素复合膜和复合片的制备方法。所述碳纳米管为单壁或多壁碳纳米管,离子液体主要由功能化咪唑及苯并噻唑类离子液体组成,包括乙基纤维素在内的衍生纤维素作为成膜剂/稀释剂。本发明采用自然成型或压片法将碳纳米管、离子液体和衍生纤维素混合物分别制成复合膜或复合片；所涉及的制备工艺简单,条件温和,易于推广,适合规模化制备。所得复合膜或复合片兼具离子液体和碳纳米管的功能。复合膜或复合片表面具有强疏水性,在水环境中不易崩解；其中的离子液体与碳纳米管结合稳定,在与水持续接触过程中不会流失。此类复合膜和复合片具有理想的环境友好性和循环使用性。(The invention discloses a preparation method of a carbon nano tube-ionic liquid-derived cellulose composite membrane and a composite sheet. The carbon nano tube is a single-wall or multi-wall carbon nano tube, the ionic liquid mainly comprises functionalized imidazole and benzothiazole ionic liquid, and derivative cellulose including ethyl cellulose is used as a film forming agent/diluent. The invention adopts a natural molding or tabletting method to respectively prepare the carbon nano tube, the ionic liquid and the derivative cellulose mixture into a composite film or a composite sheet; the preparation process is simple, mild in condition, easy to popularize and suitable for large-scale preparation. The obtained composite film or composite sheet has the functions of ionic liquid and carbon nano tubes. The surface of the composite film or the composite sheet has strong hydrophobicity and is not easy to disintegrate in a water environment; the ionic liquid and the carbon nano tube are combined stably and cannot be lost in the continuous contact process with water. The composite film and the composite sheet have ideal environmental friendliness and recycling property.)

1. A carbon nanotube-ionic liquid-derived cellulose composite membrane is characterized in that the carbon nanotube, the ionic liquid and the derived cellulose used as a film forming agent are compounded by a simple physical mixing method, and the carbon nanotube-ionic liquid-derived cellulose composite membrane comprises the following specific steps:

(1) mixing the carbon nano tube and the ionic liquid according to a mass ratio (mg/mg) of 1/1-1/20, and fully combining the carbon nano tube and the ionic liquid; adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 into the mixture for dilution, finally adding ethanol with the mass-volume ratio (g/ml) of 0.3/50-0.3/100 into the mixture of the three, and ultrasonically oscillating at room temperature to uniformly disperse the system;

(2) continuously evaporating the uniform mixed system formed in the step (1) under a vacuum condition to remove ethanol, and finally naturally forming the carbon nano tube-ionic liquid-derived cellulose composite membrane on a smooth and clean plane.

2. A carbon nanotube-ionic liquid-derived cellulose composite sheet is characterized in that the carbon nanotube, the ionic liquid and the derived cellulose used as a diluent are pressed into sheets by a simple physical mixing method, and the carbon nanotube-ionic liquid-derived cellulose composite sheet comprises the following specific steps:

(1) mixing the carbon nano tube and the ionic liquid according to a mass ratio (mg/mg) of 1/1-1/20, and fully combining the carbon nano tube and the ionic liquid; adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 into the mixture for dilution, fully and uniformly grinding the mixture, and sieving the mixture by a 200-mesh sieve;

(2) and placing the sieved mixture powder into a stainless steel pressing die, and pressing and forming under the pressure of 5-20 MPa to obtain the carbon nanotube-ionic liquid-derived cellulose composite sheet.

3. The carbon nanotube-ionic liquid-derivatized cellulose composite membrane and composite sheet according to claims 1 and 2, wherein the carbon nanotube and the ionic liquid are physically combined and uniformly mixed with the film forming agent/diluent to form the composite membrane or the composite sheet, and the ionic liquid mainly comprises imidazole or benzothiazole ionic liquids with different alkyl substituted chain lengths and anions.

4. The method for preparing the carbon nanotube-ionic liquid-cellulose composite membrane and the composite sheet as claimed in claims 1 and 2, wherein the carbon nanotube comprises a single-walled carbon nanotube or a multi-walled carbon nanotube.

5. The carbon nanotube-ionic liquid-derivatized cellulose composite film and the composite sheet as claimed in claims 1 and 2, wherein the film forming agent/diluent is derivatized cellulose including ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose.

6. The carbon nanotube-ionic liquid-derivatized cellulose composite membrane and the preparation method of the composite membrane as claimed in claims 1 and 2, wherein the mass ratio (mg/mg) of the ionic liquid to the carbon nanotube is 1/1-1/20.

7. The carbon nanotube-ionic liquid-derivatized cellulose composite membrane and the preparation method of the composite sheet according to claims 1 and 2, wherein the mass ratio (g/g) of the ionic liquid-carbon nanotube mixture to the film forming agent/diluent is 0.05/0.25-0.15/0.15.

8. The method of claim 1, wherein the solvent is ethanol.

9. The method for preparing the carbon nanotube-ionic liquid-derivatized cellulose composite sheet as claimed in claim 2, wherein the sheet forming pressure is in the range of 5 to 20 MPa.

Technical Field

The invention belongs to the technical field of composite materials, and particularly relates to the field of ionic liquid and carbon nanotube composite materials; it relates to a method for preparing composite film and composite sheet mainly using carbon nano tube and ionic liquid as functional components.

Background

As a special nano material, carbon nanotubes have been studied for the past 30 years to show excellent electrical, mechanical, thermal, chemical and mechanical properties. It can be classified into single-walled carbon nanotubes and multi-walled carbon nanotubes according to the classification of the number of graphite sheets. The single-walled carbon nanotube is formed by coiling single-walled flake graphite, and the single-walled carbon nanotubes with different diameters are sleeved by multi-walled carbon nanotubes, and the distance between layers is about 0.34 nm. Due to the unique and stable hollow tube cavity structure, the larger length-diameter ratio and the flexible and changeable functional mode, the composite material can be widely applied to gas separation, catalytic degradation and adsorption of water quality organic pollutants (such as dioxin, chlorobenzene, antibiotics and the like), heavy metal ions from different sources and other environment harmful residues in the technical field.

Ionic liquids are of particular interest for their environmentally friendly physical and chemical properties, such as low vapor pressure, high solvent capacity, chemical stability, good electrical conductivity, versatility, which make them a significant advantage over traditional organic solvents. At present, various functionalized ionic liquids are widely applied to the fields related to catalysis, separation, electrochemistry, nano materials, polymer science, biomass processing, lubricants and the like, wherein certain processes can be operated on an industrial scale. Ionic liquids are considered one of the industrially potential green solvents, since their very low volatility prevents their emission into the environment. In addition, the ionic liquid is immobilized in different modes, so that the ionic liquid is recovered and recycled, and the consumption and the loss of the ionic liquid are further reduced.

Cellulose is one of polysaccharides with the highest global yield, belongs to natural degradable products, has no harm, and different derivative products of the cellulose are widely used as fine chemical auxiliary materials; among them, a series of derivatives represented by ethyl cellulose have very excellent adhesion and film-forming properties, and stable chemical properties and biocompatibility, and thus are increasingly used in the technical field.

Disclosure of Invention

The invention aims to provide a preparation method of a composite film and a composite sheet, which take ionic liquid and carbon nano tubes as functional components; the method has the advantages of simple process, mild conditions, convenient operation, easy popularization and no use of special equipment. The derivative cellulose is used for compounding the ionic liquid and the carbon nano tube in the form of a film or a sheet in simple steps, so that the defects of high cost, difficult recovery, difficult recycling and the like when the derivative cellulose and the carbon nano tube are used independently at present are overcome greatly, and the immobilization means and the application form of the conventional ionic liquid are expanded in a convenient, flexible and easily-amplified manner. The good physical and chemical properties of the carbon nano tube-ionic liquid-derivative cellulose composite membrane and the composite sheet show obvious combination advantages, and the overall properties, the functional integration and the mechanical strength of the carbon nano tube-ionic liquid-derivative cellulose composite membrane and the composite sheet are superior to those of the ionic liquid (or carbon nano tube) -derivative cellulose composite material prepared under the same conditions. The composite film has smooth appearance and good homogeneity, and is convenient to cut; the composite sheet has regular appearance and saves storage space in volume; both are easy to realize large-scale preparation and multiple use. The water-soluble organic silicon dioxide gel has the characteristics of strong hydrophobicity, no problems of disintegration and component loss in an aqueous solution, no pollution to environment and objects, environmental friendliness and good reusability.

The technical scheme is as follows: in order to realize the purpose, the preparation method of the composite membrane and the composite sheet which are composed of the ionic liquid, the carbon nano tube and the derivative cellulose is provided:

an ionic liquid and carbon nano tube-derived cellulose composite membrane is characterized in that carbon nano tubes and the ionic liquid are formed by simply physically combining, uniformly dispersing in a solvent together with a film forming agent and then recovering the solvent, and the preparation method comprises the following specific steps:

(1) mixing the carbon nano tube and the ionic liquid according to a mass ratio (mg/mg) of 1/1-1/20, and fully combining the carbon nano tube and the ionic liquid; adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 into the mixture for dilution, finally adding ethanol with the mass-volume ratio (g/ml) of 0.3/50-0.3/100 into the mixture of the three, and ultrasonically oscillating at room temperature to uniformly disperse the system;

(2) continuously evaporating the uniform mixed system formed in the step (1) under a vacuum condition to remove ethanol, and finally naturally forming the carbon nano tube-ionic liquid-derived cellulose composite membrane on a smooth and clean plane.

The ionic liquid-carbon nanotube-derivative cellulose composite sheet is characterized in that the carbon nanotube and the ionic liquid are prepared by simple physical combination and tabletting together with a diluent, and the preparation method comprises the following specific steps:

(1) mixing the carbon nano tube and the ionic liquid according to a mass ratio (mg/mg) of 1/1-1/20, and fully combining the carbon nano tube and the ionic liquid; adding derivative cellulose with the mass ratio (g/g) of 0.05/0.25-0.15/0.15 into the mixture for dilution, fully and uniformly grinding the mixture, and sieving the mixture by a 200-mesh sieve;

(2) and (3) placing the sieved mixed powder into a stainless steel pressing die, and pressing and forming under the pressure of 5-20 MPa to obtain the carbon nanotube-ionic liquid-derived cellulose composite sheet.

The carbon nanotube-ionic liquid-derivative cellulose composite membrane and the composite sheet have the advantages that the ionic liquid mainly comprises imidazole and benzothiazole ionic liquids with different alkyl substituted chain lengths and anions, and the ionic liquids comprise but are not limited to the structures shown in the table 1.

Table 1 ionic liquid structures encompassed by the present patent

According to the preparation method of the carbon nanotube-ionic liquid-derivative cellulose composite membrane and the composite sheet, the carbon nanotube comprises a single-walled carbon nanotube or a multi-walled carbon nanotube.

The carbon nanotube-ionic liquid-derived cellulose composite membrane and the composite sheet are characterized in that: the film forming/diluent used is a derivatized cellulose including, but not limited to, ethyl cellulose, methyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose.

According to the preparation method of the multi-walled carbon nanotube-ionic liquid-derived cellulose composite membrane and the composite sheet, the mass ratio (mg/mg) of the ionic liquid to the carbon nanotube is 1/1-1/20.

According to the preparation method of the carbon nanotube-ionic liquid-derived cellulose composite membrane and the composite sheet, the mass ratio (g/g) of the ionic liquid carbon nanotube mixture to the film forming agent is 0.05/0.25-0.15/0.15.

In the preparation method of the carbon nanotube-ionic liquid-derived cellulose composite membrane, the solvent is ethanol.

According to the preparation method of the carbon nanotube-ionic liquid-derived cellulose composite sheet, the sheet forming pressure range includes, but is not limited to, 5-20 MPa.

Drawings

FIG. 1 shows a carbon nanotube multi-walled carbon nanotube [ C ] having a thickness of 0.1mm₄Bth][PF₆]-the ubiquitous appearance of the ethylcellulose composite film (a: front view, b: side view)

FIG. 2 shows a multi-walled carbon nanotube [ C ] having a diameter of 13mm and a thickness of 2mm₄Bth][PF₆]Appearance of ethylcellulose composite sheet

FIG. 3(a) shows a multi-walled carbon nanotube- [ C ]₄Bth][PF₆]Photograph of ethyl cellulose composite film in contact with water and (b) contact Angle CA image (hydrophobic Angle: 89.33 degree)

FIG. 4 shows a carbon nanotube-multiwalled carbon nanotube- [ C ]₄Bth][PF₆]Scanning electron micrographs of the ethylcellulose composite sheet (a: front view, b: cut view; wherein the carbon nanotubes are tubular and the ethylcellulose surface is approximately spherical); from the front and the section view, the ionic liquid, the multi-walled carbon nanotube and the ethyl cellulose can be seen to be uniformly mixed

FIG. 5 is a multi-walled carbon nanotube- [ C ]₄Bth][PF₆]Zeta potential result of composite ethylcellulose film and composite sheet (Zeta potential value of material surface 0 when pH is 3.20)

Detailed Description

The following examples are given for the purpose of illustrating the invention in detail, but are not to be construed as limiting the scope of the invention. The endpoints of the ranges and any values recited herein are not limited to the precise range and value, and such ranges are to be understood as encompassing values close to the value of such ranges, and insubstantial modifications and adaptations of those values by those skilled in the art in light of this disclosure are intended to be within the scope of the invention.

Example 1

The total mass is 0.05g of 1-butylbenzothiazole hexafluorophosphate Ionic liquid ([ C ]₄Bth][PF₆]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.05/0.25, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min, mixing, evaporating under vacuum to remove solvent, and forming multi-walled carbon nanotube- [ C ] on smooth clean plane₄Bth][PF₆]-an ethylcellulose composite membrane.

Example 2

0.1g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass₄Bth][PF₆]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.1/0.2, adding the mixture into 100ml round-bottom flask, adding 50ml anhydrous ethanol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane₄Bth][PF₆]-an ethylcellulose composite membrane.

Example 3

0.15g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass₄Bth][PF₆]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum condition to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane₄Bth][PF₆]-an ethylcellulose composite membrane.

The contact angle test was performed on the composite film prepared in example 10, and the test conditions and results are shown in table 2.

TABLE 2 Multi-walled carbon nanotubesPipe [ C ]₄Bth][PF₆]-ethyl cellulose composite film contact angle test condition and result

The composite membrane prepared in example 10 was subjected to a material surface Zeta potential test, and the test conditions and results are shown in table 3.

TABLE 3 Multi-walled carbon nanotubes [ C ]₄Bth][PF₆]Zeta potential test conditions and results for-ethyl cellulose composite membrane

Example 4

The total mass of 0.15g of benzothiazole tetrafluoroborate ionic liquid ([ HBth ]][BF₄]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with hydroxypropyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml anhydrous ethanol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum to remove solvent, and forming multi-walled carbon nanotube- [ HBth ] on smooth clean plane][BF₄]-hydroxypropyl cellulose composite membranes.

Example 5

Benzothiazole methanesulfonate ([ HBth ] in a total mass of 0.15g][CH₃SO₃]) Mixing with single-walled carbon nanotubes in a mass ratio of 1/1 to fully combine the two; mixing with carboxymethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethanol, ultrasonic treating at room temperature for 10min to disperse the system uniformly, evaporating under vacuum to remove solvent, and forming single-walled carbon nanotube- [ HBth ] on smooth clean surface][CH₃SO₃]-carboxymethyl cellulose composite membranes.

Example 6

The total mass of 0.15g of benzothiazole trifluoromethanesulfonate ([ HBth ]][CF₃SO₃]) Mixing with single-walled carbon nanotubes in a mass ratio of 1/1 to fully combine the two; then evenly mixing with hydroxypropyl cellulose in a mass ratio (g/g) of 0.15/0.15, and mixingAdding the mixture of the three into 100ml round bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating to remove the solvent under vacuum condition, and forming single-walled carbon nanotube- [ HBth ] on a smooth and clean plane][CF₃SO₃]-hydroxypropyl cellulose composite membranes.

Example 7

Mixing benzothiazole tosyloxy salt ([ HBth ] [ PTSA ]) with the total mass of 0.15g and the single-wall carbon nanotube in the mass ratio of 1/1 to combine the two fully; then evenly mixing the mixture with ethyl cellulose according to the mass ratio (g/g) of 0.15/0.15, adding the mixture of the three into a 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, carrying out ultrasonic treatment at room temperature for 10min to evenly disperse the system, evaporating the solvent under the vacuum condition, and forming the single-walled carbon nanotube- [ HBth ] [ PTSA ] -ethyl cellulose composite membrane on a smooth clean plane.

Example 8

1-butyl-3-methylimidazolium hexafluorophosphate ([ C ] in a total mass of 0.15g₄mim][PF₆]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with ethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum condition to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane₄mim][PF₆]-an ethylcellulose composite membrane.

Example 9

1-Ethyl-3-methylimidazolium tetrafluoroborate ([ C ]) in a total mass of 0.15g₂mim][BF₄]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with carboxymethyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml absolute ethyl alcohol, performing ultrasonic treatment at room temperature for 10min to disperse the system uniformly, evaporating under vacuum condition to remove solvent, and forming multi-wall carbon nanotube- [ C ] on smooth clean plane₂mim][BF₄]-carboxymethyl cellulose composite membranes.

Example 10

The total mass of 0.15g of 1-hexyl-3-methylimidazolium methanesulfonate ([ Hmim)][CH₃SO₃]) Mixing with multi-wall carbon nano-tube in a mass ratio of 1/1, and fully combining the two; mixing with hydroxypropyl cellulose at mass ratio (g/g) of 0.15/0.15, adding the mixture into 100ml round-bottom flask, adding 50ml anhydrous ethanol, ultrasonically treating at room temperature for 10min to disperse the system uniformly, evaporating under vacuum to remove solvent, and forming multi-wall carbon nanotube- [ Hmim ] on smooth and clean surface][CH₃SO₃]-hydroxypropyl cellulose composite membranes.

Example 11

0.05g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass₄Bth][PF₆]) Mixing with multi-wall carbon nano-tubes according to a mass ratio of 1/1, then mixing with ethyl cellulose according to a mass ratio (g/g) of 0.05/0.25 in a mortar, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 15MPa to obtain the multi-walled carbon nanotube- [ C ]₄Bth][PF₆]-an ethylcellulose compact.

Example 12

0.1g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass₄Bth][PF₆]) Mixing with multi-wall carbon nano-tubes according to a mass ratio of 1/1, then mixing with ethyl cellulose according to a mass ratio (g/g) of 0.1/0.2 in a mortar, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 15MPa to obtain the multi-walled carbon nanotube- [ C ]₄Bth][PF₆]-an ethylcellulose compact.

Example 13

0.15g of 1-butylbenzothiazole hexafluorophosphate ionic liquid ([ C ] in total mass₄Bth][PF₆]) Mixing with multi-wall carbon nano-tubes according to a mass ratio of 1/1, then mixing with ethyl cellulose according to a mass ratio (g/g) of 0.15/0.15 in a mortar, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 15MPa to obtain the multi-walled carbon nanotube- [ C ]₄Bth][PF₆]-ethyl radicalA cellulose composite sheet.

Example 14

The total mass of 0.15g of benzothiazole tetrafluoroborate ionic liquid ([ HBth ]][BF₄]) Mixing with multi-wall carbon nano-tubes according to a mass ratio of 1/1, then mixing with hydroxypropyl cellulose according to a mass ratio (g/g) of 0.15/0.15 in a mortar, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 15MPa to obtain the multi-walled carbon nanotube- [ HBth [ ]][BF₄]-a hydroxypropyl cellulose compact.

Example 15

Benzothiazole methanesulfonate ([ HBth ] in a total mass of 0.15g][CH₃SO₃]) Mixing with single-walled carbon nanotubes in a mass ratio of 1/1, then mixing with carboxymethyl cellulose in a mortar in a mass ratio (g/g) of 0.15/0.15, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel pressing mold, and pressing and molding under the pressure of 20MPa to obtain the single-walled carbon nanotube- [ HBth [ ]][CH₃SO₃]-a carboxymethyl cellulose composite sheet.

Example 16

The total mass of 0.15g of benzothiazole trifluoromethanesulfonate ([ HBth ]][F₃CSO₃]) Mixing with single-walled carbon nanotubes in a mass ratio of 1/1, mixing with hydroxypropyl cellulose in a mortar in a mass ratio (g/g) of 0.15/0.15, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel pressing mold, and pressing and molding under the pressure of 20MPa to obtain the single-walled carbon nanotube- [ HBth [ ]][F₃CSO₃]-a hydroxypropyl cellulose compact.

Example 17

Mixing benzothiazole tosyloxy salt ([ HBth ] [ PTSA ]) with the total mass of 0.15g and single-walled carbon nanotubes according to the mass ratio of 1/1, then mixing the mixture with ethyl cellulose according to the mass ratio (g/g) of 0.15/0.15 in a mortar, uniformly grinding the mixture, and sieving the mixture by a 200-mesh sieve; and putting the mixture powder into a stainless steel pressing die, and pressing and molding under the pressure of 18MPa to obtain the single-walled carbon nanotube- [ HBth ] [ PTSA ] -ethyl cellulose composite sheet.

Example 18

1-butyl-3-methylimidazolium hexafluorophosphate ([ C ] in a total mass of 0.15g₄mim][PF₆]) Mixing with multi-wall carbon nano-tubes according to a mass ratio of 1/1, then mixing with ethyl cellulose according to a mass ratio (g/g) of 0.15/0.15 in a mortar, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 20MPa to obtain the multi-walled carbon nanotube- [ C ]₄mim][PF₆]-an ethylcellulose compact.

Example 19

1-Ethyl-3-methylimidazolium tetrafluoroborate ([ C ]) in a total mass of 0.05g₂mim][BF₄]) Mixing with multi-wall carbon nano-tubes according to a mass ratio of 1/1, then mixing with carboxymethyl cellulose according to a mass ratio (g/g) of 0.05/0.25 in a mortar, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 10MPa to obtain the multi-walled carbon nanotube- [ C ]₂mim][BF₄]-a carboxymethyl cellulose composite sheet.

Example 20

The total mass of 0.05g of 1-hexyl-3-methylimidazolium methanesulfonate ([ Hmim)][CH₃SO₃]) Mixing with multi-wall carbon nano-tubes according to a mass ratio of 1/1, then mixing with hydroxypropyl cellulose according to a mass ratio (g/g) of 0.05/0.25 in a mortar, grinding uniformly, and sieving with a 200-mesh sieve; placing the mixture powder into a stainless steel sheet pressing die, and pressing and molding under the pressure of 12MPa to obtain the multi-walled carbon nanotube- [ Hmim [ ]][CH₃SO₃]-a hydroxypropyl cellulose compact.