CN108503896A - A kind of carbonization bacteria cellulose/carbon nanotube membrane material and preparation method thereof - Google Patents
A kind of carbonization bacteria cellulose/carbon nanotube membrane material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of carbonization bacteria cellulose/carbon nanotube membrane materials and preparation method thereof, which includes：1）Prepare carboxylic carbon nano-tube nano dispersion fluid；2）Prepare bacteria cellulose/carboxylic carbon nano-tube aeroge；3）Carbonization bacteria cellulose/carbon nano-tube film is prepared in carbonization treatment.The present invention not only ensures the integrality of carbonization bacteria cellulose/carbon nano-tube film and good mechanical property, and possesses high electrical conductance.Preparation process is simple, environmentally protective, is suitble to mass production.
Description
Technical field
The invention belongs to conductive material preparing technical field more particularly to a kind of carbonization bacteria cellulose/carbon nano-tube films
Material and preparation method thereof.
Background technology
Bacteria cellulose, which has been realized, to be commercially produced, by can scale high-performance bio fermentation technique prepare, by cheap
Bacterium metabolism synthesis is carried out to small molecular sugar, alcohol, directly obtain high purity cellulose, and be widely used in medical material, food
The industries such as product, light industry and environmental protection.Bacteria cellulose has high-purity, high-crystallinity, high polymerization degree, fine reticular structure, life
The characteristics such as object adaptability and degradability, wherein the three-dimensional porous nano fiber pliability network of bacteria cellulose and abundant
Surface functional group is very suitable for aeroge, the preparation of film and functionalization.Carbon nanotube possesses good mechanical property and height is led
Electric rate (106S/m), thermal conductivity is higher than 3000W/ (mK), with carbonization bacteria cellulose good compatibility.Bacteria cellulose aeroge with
It is compound that highly conductive flexible carbon nano tube can reach nanoscale, is formed in the interior thereof three-dimensional conductive network, and can significantly carry
The mechanical performance of high composite material.By carbon nanotube encapsulation into the subtle three-dimensional network of carbonization bacteria cellulose, can further carry
Conductivity, thermal conductivity and the mechanical property of high-carbon three-dimensional network.Therefore, high conductivity carbon nanotube and carbonization bacteria cellulose net
The combination of network provides new thinking for the design of three-dimensional carbon conductive network.
Currently, the method for preparing bacteria cellulose/carbon nano-tube compound film is broadly divided into four kinds：1) in point of carbon nanotube
Acetobacter xylinum is accessed in dispersion liquid, growth in situ bacteria cellulose obtains bacteria cellulose/carbon nano-tube compound film, the technique system
Standby process is complicated, and the period is long；2) quiet after further being mixed with carbon nanotube by trifluoroacetic acid equal solvent dissolution of bacteria cellulose
Electrospun forms bacteria cellulose/carbon nano-tube compound film, and the solvent toxicity of usual dissolution of bacteria cellulose is larger, to environment dirt
Dye is big；3) handle blocky bacteria cellulose using physical means such as refiner or mulsers to prepare its emulsion, further with
Carbon nanotube mixes, bacteria cellulose/carbon nano-tube compound film is prepared by filtering or depositing, processing damage bacterium
The original three-dimensional net structure of cellulose；4) blocky bacteria cellulose is immersed in the dispersion liquid of carbon nanotube for a long time to prepare
Bacteria cellulose/carbon nano-tube compound film, with the increase of soaking time, the content of carbon nanotube increases, but most of carbon
Nanotube deposition is easy to peel off from surface on bacteria cellulose aquagel surface.In addition, bacteria cellulose is insulator,
Carbonization bacteria cellulose, which is prepared, in pyrolysis bacteria cellulose can further increase conductivity.Carbon nanotube scale is uniform
It is that structure pyrolysis bacteria cellulose/carbon nanotube is compound to be dispersed in bacteria cellulose aeroge and neutralize suitable pyrolysis Carbonization Conditions
The key of film, concerning strong three-dimensional conductive network can be formed.
Invention content
For prior art preparation period length, the three-dimensional net structure and carbon that have pollution to environment, destroy bacteria cellulose
Nanotube is easy to the shortcomings of surface is peeled off, the object of the present invention is to provide a kind of carbonization bacteria cellulose/carbon nanotube membrane material,
Carbon nanotube is uniform to be arranged in carbon film, has many advantages, such as that homogeneous and conductivity is high.It is a further object of the present invention to provide
A kind of preparation method of above-mentioned carbonization bacteria cellulose/carbon nanotube membrane material, simple production process is environmental-friendly, at low cost
It is honest and clean, it is suitble to mass production.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is：
A kind of preparation method of carbonization bacteria cellulose/carbon nanotube membrane material, includes the following steps：
1) carboxylic carbon nano-tube is dispersed in the aqueous solution with surfactant, is divided using surfactant
Carboxylic carbon nano-tube is dissipated, ultrasonic cell disruption instrument is reused and dispersion liquid is crushed, obtain carboxylic carbon nano-tube nanometer point
Dispersion liquid；
2) after drawing the moisture in bacteria cellulose aquagel with water-absorbent material, then it is immersed in the high stable of step 1)
Carboxylic carbon nano-tube nano dispersion fluid in, repetitive operation, obtain the uniform black for being dispersed in bacteria cellulose of carbon nanotube
Composite hydrogel washs composite hydrogel repeatedly, the carbon nanotube aggregate until removing surfactant and hydrogel surface,
Freeze-drying, is prepared bacteria cellulose/carboxylic carbon nano-tube aeroge；
3) by the bacteria cellulose in step 2)/carboxylic carbon nano-tube aeroge under inert atmosphere or reducing atmosphere
Carbonization treatment is carried out, carbonization bacteria cellulose/carbon nano-tube film is prepared.
In step 1), carbon nanotube is single wall/multi-walled carbon nanotube, 2~200nm of caliber, 1~100 μm of length.
In step 1), carbon nano-tube solution mass fraction is 0.01%~10%.
Surfactant in step 1) is neopelex, cetyl trimethylammonium bromide, polyethylene pyrrole
Pyrrolidone, one or more of sodium lignin sulfonate etc..
In step 1), surfactant qualities score is 0.1%~5%.
In step 1), ultrasonication processing power is 200~1000W, and the time is >=15min.
In step 2), immersion total time is 5~48h, blots number >=2 time.
In step 2), freeze-dryer is -25~-60 DEG C, and sublimation drying is 10~48h.
In step 3), Carbonization Conditions are 300~500 DEG C, and constant temperature time is 0.5~5h.
A kind of carbonization bacteria cellulose/carbon nanotube membrane material, by the carbonization bacteria cellulose described in above-mentioned technical proposal/
The preparation method of carbon nanotube membrane material is prepared.
Advantageous effect：Compared with prior art, carbonization of the invention bacteria cellulose/carbon nanotube membrane material and its preparation
Method has the advantage that：
1) polymolecularity being stabilized can be prepared by being combined aid dispersion using ultrasonication and surfactant
Carboxylic carbon nano-tube suspension.One-dimensional tubular structure, and the surface functional group meeting of adjacent carbon nanotubes is presented in carbon nanotube
There is interaction, this is the basic reason that carbon nanotube is easily reunited, and surfactant aid dispersion carboxylic carbon nano-tube can
Improve the dispersibility of carbon nanotube to a certain extent, but still can not meet carbon nanotube and enter the netted knot of bacterial cellulose three-dimensional
To the requirement of its dispersibility in structure.Ultrasonication can open the interaction of adjacent carbon nanotubes, and mating surface activating agent is real
The polymolecularity and high stability of existing carboxylic carbon nano-tube.
2) utilize water-absorbent material that the moisture of bacteria cellulose aquagel is sucked out, then in the carboxylic carbon nano-tube of high dispersive
It is impregnated in suspension, repeated multiple times, this immersion technology can enable a large amount of carboxylic carbon nano-tube enter bacteria cellulose
In 3 D pore canal and it is uniform be dispersed in duct, be sucked out moisture process simultaneously remove the most carbon nanotube aggregate in surface,
Be conducive to fresh dispersion liquid to enter inside bacteria cellulose, in addition, a large amount of hydroxyl in bacteria cellulose surface has water absorbing capacity
Power enters for fresh carboxylic carbon nano-tube aqueous dispersion and provides sufficient power in bacterial cellulose three-dimensional network,
The absorption and insertion for being conducive to carboxylic carbon nano-tube, to improve injection of the carbon nanotube inside bacteria cellulose aquagel
Amount.
3) surface hydroxyl of the carboxylic carbon nano-tube of polymolecularity and bacteria cellulose has strong hydrogen bond action so that
Bacteria cellulose is firmly combined together with carboxylic carbon nano-tube, to realize that being dispersed in for carbon nanotube stable homogeneous is thin
In fungin network.
4) bacteria cellulose is insulator, there is its limitation when preparing conductive material, and bacteria cellulose is conductive after carbonization
Rate significantly increases, but mechanical property is very poor, and the present invention is carbonized under inertia or reducing atmosphere and carbon nanotube is prepared
The three-dimensional porous carbonization bacteria cellulose film of uniform arrangement, not only ensures the complete of carbonization bacteria cellulose/carbon nano-tube film
Property and good mechanical property, and possess high electrical conductance.
5) preparation process is simple, environmentally protective, is suitble to mass production.
Description of the drawings
Fig. 1 is that the digital of carbonization bacteria cellulose/carboxylic carbon nano-tube film being prepared in case study on implementation 1~4 is shone
Piece figure；
Fig. 2 is the scanning electron microscope (SEM) photograph for the carbonization bacteria cellulose/carboxylic carbon nano-tube film being prepared in case study on implementation 2
(surface and section).
Specific implementation mode
The present invention is described further With reference to embodiment.Technical solution of the present invention is not limited to following
Cited specific implementation mode further includes the arbitrary combination between each specific implementation mode.
Embodiment 1
A kind of preparation method of carbonization bacteria cellulose/carbon nano-tube film：By 7~15nm of diameter, the carboxylic that 5~20 μm of length
Base multi-walled carbon nano-tube is dispersed in the aqueous solution of surfactant cetyl trimethylammonium bromide 0.3wt%, is obtained dense
0.05wt% functionalized multi-wall carbonnanotubes aqueous solutions are spent, ultrasonic cell disruption instrument is reused and is crushed and disperse, power 600W,
Ultrasonic time is 10min, and the functionalized multi-wall carbonnanotubes nano dispersion fluid of high stable is finally prepared.Utilize conventional fibre
The moisture of bacteria cellulose aquagel is sucked out in plain filter paper, is immersed in the carboxylated multi-wall carbon nano-tube of high stable again at room temperature
In pipe nano dispersion fluid, multi-walled carbon nanotube dispersion liquid is fully sucked, realizes multi-walled carbon nanotube in bacteria cellulose aquagel
In uniform distribution.It is absorbed water to the hydrogel of bacteria cellulose using conventional fibre element filter paper, then in multi-wall carbon nano-tube
It is impregnated in pipe dispersion liquid, injection multi-walled carbon nanotube is in the network of bacteria cellulose, repetitive operation 3 times, and total soaking time is
22h obtains the uniform black composite hydrogel for being dispersed in bacteria cellulose of multi-walled carbon nanotube, repeatedly with deionized water or ethyl alcohol
Bacteria cellulose/multi-walled carbon nanotube composite hydrogel 3 times is washed, the multi wall until removing surfactant and hydrogel surface
Carbon nanotube aggregate is freeze-dried for 24 hours for -50 DEG C in freeze-dryer, and functionalized multi-wall carbonnanotubes content, which is prepared, is
The bacteria cellulose of 14.6wt%/functionalized multi-wall carbonnanotubes aeroge.Bacteria cellulose/functionalized multi-wall carbonnanotubes gas
Gel carries out carbonization treatment in tube furnace under nitrogen atmosphere.Carbonization Conditions are：In 350 DEG C of constant temperature 1h, it is thin that carbonization is prepared
Fungin/multi-wall carbon nano-tube periosteum is labeled as a, and the content of carbon nanotube is about 34.7wt%.
Embodiment 2
A kind of preparation method of carbonization bacteria cellulose/carbon nano-tube film：By 7~15nm of diameter, the carboxylic that 5~20 μm of length
Base multi-walled carbon nano-tube is dispersed in the aqueous solution of surfactant cetyl trimethylammonium bromide 0.3wt%, is obtained dense
0.05wt% functionalized multi-wall carbonnanotubes aqueous solutions are spent, ultrasonic cell disruption instrument is reused and is crushed and disperse, power 600W,
Ultrasonic time is 10min, and the functionalized multi-wall carbonnanotubes nano dispersion fluid of high stable is finally prepared.Utilize conventional fibre
The moisture of bacteria cellulose aquagel is sucked out in plain filter paper, is immersed in the carboxylated multi-wall carbon nano-tube of high stable again at room temperature
In pipe nano dispersion fluid, multi-walled carbon nanotube dispersion liquid is fully sucked, realizes multi-walled carbon nanotube in bacteria cellulose aquagel
In uniform distribution.It is absorbed water to the hydrogel of bacteria cellulose using conventional fibre element filter paper, then in multi-wall carbon nano-tube
It is impregnated in pipe dispersion liquid, injection multi-walled carbon nanotube is in the network of bacteria cellulose, repetitive operation 4 times, and total soaking time is
13h obtains the uniform black composite hydrogel for being dispersed in bacteria cellulose of multi-walled carbon nanotube, repeatedly with deionized water or ethyl alcohol
Bacteria cellulose/multi-walled carbon nanotube composite hydrogel 3 times is washed, the multi wall until removing surfactant and hydrogel surface
Carbon nanotube aggregate is freeze-dried for 24 hours for -50 DEG C in freeze-dryer, and functionalized multi-wall carbonnanotubes content, which is prepared, is
The bacteria cellulose of 14.6wt%/functionalized multi-wall carbonnanotubes aeroge.Bacteria cellulose/functionalized multi-wall carbonnanotubes gas
Gel carries out carbonization treatment in tube furnace under nitrogen atmosphere.Carbonization Conditions are：In 400 DEG C of constant temperature 0.5h, carbonization is prepared
Bacteria cellulose/multi-wall carbon nano-tube periosteum is labeled as b, and the content of carbon nanotube is about 41.9wt%.
Embodiment 3
A kind of preparation method of carbonization bacteria cellulose/carbon nano-tube film：By 30~50nm of diameter, 10~20 μm of length
Functionalized multi-wall carbonnanotubes are dispersed in the aqueous solution of surfactant sodium dodecyl base benzene sulfonic acid sodium salt 0.3wt%, obtain concentration
0.05wt% functionalized multi-wall carbonnanotubes aqueous solutions, reuse the broken dispersion of ultrasonic cell disruption instrument, and power 400W surpasses
The sound time is 40min, and the functionalized multi-wall carbonnanotubes nano dispersion fluid of high stable is finally prepared.Utilize conventional fibre element
The moisture of bacteria cellulose aquagel is sucked out in filter paper, is immersed in the functionalized multi-wall carbonnanotubes of high stable again at room temperature
In nano dispersion fluid, multi-walled carbon nanotube dispersion liquid is fully sucked, realizes multi-walled carbon nanotube in bacteria cellulose aquagel
Uniform distribution.It is absorbed water to the hydrogel of bacteria cellulose using conventional fibre element filter paper, then in multi-walled carbon nanotube
It being impregnated in dispersion liquid, injection multi-walled carbon nanotube is in the network of bacteria cellulose, repetitive operation 2 times, and total soaking time is 8h,
The uniform black composite hydrogel for being dispersed in bacteria cellulose of multi-walled carbon nanotube is obtained, is washed repeatedly with deionized water or ethyl alcohol
Bacteria cellulose/multi-walled carbon nanotube composite hydrogel 4 times, the multi wall carbon until removing surfactant and hydrogel surface are received
Mitron aggregate is freeze-dried for 24 hours for -50 DEG C in freeze-dryer, and functionalized multi-wall carbonnanotubes content, which is prepared, is
The bacteria cellulose of 13.9wt%/functionalized multi-wall carbonnanotubes aeroge.Bacteria cellulose/functionalized multi-wall carbonnanotubes gas
Gel carries out carbonization treatment in tube furnace under nitrogen atmosphere.Carbonization Conditions are：In 450 DEG C of constant temperature 0.5h, carbonization is prepared
Bacteria cellulose/multi-wall carbon nano-tube periosteum is labeled as c, and the content of carbon nanotube is about 47.9wt%.
Embodiment 4
A kind of preparation method of carbonization bacteria cellulose/carbon nano-tube film：By 10~20nm of diameter, 5~20 μm of length
Functionalized multi-wall carbonnanotubes are dispersed in the aqueous solution of surfactant sodium lignin sulfonate 0.2wt%, obtain concentration
0.05wt% functionalized multi-wall carbonnanotubes aqueous solutions, reuse the broken dispersion of ultrasonic cell disruption instrument, and power 600W surpasses
The sound time is 60min, and the functionalized multi-wall carbonnanotubes nano dispersion fluid of high stable is finally prepared.Utilize conventional fibre element
The moisture of bacteria cellulose aquagel is sucked out in filter paper, is immersed in the functionalized multi-wall carbonnanotubes of high stable again at room temperature
In nano dispersion fluid, multi-walled carbon nanotube dispersion liquid is fully sucked, realizes multi-walled carbon nanotube in bacteria cellulose aquagel
Uniform distribution.It is absorbed water to the hydrogel of bacteria cellulose using conventional fibre element filter paper, then in multi-walled carbon nanotube
It is impregnated in dispersion liquid, injection multi-walled carbon nanotube is in the network of bacteria cellulose, repetitive operation 4 times, and total soaking time is
22h obtains the uniform black composite hydrogel for being dispersed in bacteria cellulose of multi-walled carbon nanotube, repeatedly with deionized water or ethyl alcohol
Bacteria cellulose/multi-walled carbon nanotube composite hydrogel 4 times is washed, the multi wall until removing surfactant and hydrogel surface
Carbon nanotube aggregate is freeze-dried for 24 hours for -50 DEG C in freeze-dryer, and functionalized multi-wall carbonnanotubes content, which is prepared, is
The bacteria cellulose of 15wt%/functionalized multi-wall carbonnanotubes aeroge.Bacteria cellulose/functionalized multi-wall carbonnanotubes airsetting
Glue carries out carbonization treatment in tube furnace under nitrogen atmosphere.Carbonization Conditions are：In 350 DEG C of constant temperature 2h, carbonization bacterium is prepared
Cellulose/multi-wall carbon nano-tube periosteum is labeled as d, and the content of carbon nanotube is about 33.3wt%.
The number for the carbonization bacteria cellulose/carboxylic carbon nano-tube film a~d being prepared in above-mentioned case study on implementation 1~4
As shown in Figure 1, the carbon nanotube of black is successfully distributed to inside bacteria cellulose film, composite membrane presents good complete photo
Property and flexibility.To carboxylic carbon nano-tube in case study on implementation 1~4 and gained is prepared using four probe conduction testers (SDY-5)
The conductivity of carbonization bacteria cellulose/carbon nano-tube film tested.The results are shown in Table 1, in above-mentioned case study on implementation 1~4
In, carbonization bacteria cellulose/carbon nano-tube compound film that the content of carbon nanotubes that is prepared in case study on implementation 4 is about 33.3wt%
The conductivity highest of sample d, reaches 0.67S/m.
1 conductivity test result of table
| Sample | Conductivity S/m |
| Functionalized multi-wall carbonnanotubes | 80~100 |
| a | 0.21 |
| b | 0.12 |
| c | 0.29 |
| d | 0.67 |
Other than the size of carbon nanotube and dispersibility, carbon nanotube enter the content of bacteria cellulose network also with immersion
Number and immersion total time are closely bound up, and the electric conductivity and Carbonization Conditions of carbon nanotube of carboxylated itself directly affect to the end
Carbonization bacteria cellulose/carbon nano-tube compound film conductivity.Using field emission scanning electron microscope (S-4800) to case study on implementation 1
Carbonization bacteria cellulose/carbon nano-tube film that gained is prepared in~4 carries out morphology observation, it is found that multimembrane is longitudinally presented in carbon nanotube
Layer feature laterally retains three-dimensional uniform reticular structure, this is related with the shrinkage direction in bacteria cellulose network and carbonisation
System.The scanning electron microscope (SEM) photograph for the carbonization bacteria cellulose/carbon nano-tube compound film being prepared in case study on implementation 2 is as shown in Figure 2.
Claims (10)
1. a kind of preparation method of carbonization bacteria cellulose/carbon nanotube membrane material, which is characterized in that include the following steps：
1）Carboxylic carbon nano-tube is dispersed in the aqueous solution with surfactant, dispersion carboxylic is carried out using surfactant
Base carbon nano tube reuses ultrasonic cell disruption instrument and is crushed to dispersion liquid, obtains the nano-dispersed of carboxylic carbon nano-tube
Liquid；
2）After drawing the moisture in bacteria cellulose aquagel with water-absorbent material, then it is immersed in step 1）High stable carboxylic
In base carbon nano tube nano dispersion fluid, it is compound to obtain the uniform black for being dispersed in bacteria cellulose of carbon nanotube for repetitive operation
Hydrogel washs composite hydrogel repeatedly, the carbon nanotube aggregate until removing surfactant and hydrogel surface, freezing
It is dry, bacteria cellulose/carboxylic carbon nano-tube aeroge is prepared；
3）By step 2）In bacteria cellulose/carboxylic carbon nano-tube aeroge carried out under inert atmosphere or reducing atmosphere
Carbonization bacteria cellulose/carbon nano-tube film is prepared in carbonization treatment.
2. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 1）In, carbon nanotube is single wall/multi-walled carbon nanotube, 2 ~ 200nm of caliber, 1 ~ 100 μm of length.
3. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 1）In, carbon nano-tube solution mass fraction is 0.01% ~ 10%.
4. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 1）In surfactant be neopelex, cetyl trimethylammonium bromide, polyvinylpyrrolidone, wood
One or more of quality sodium sulfonate etc..
5. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 1）In, surfactant qualities score 0.1% ~ 5%.
6. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 1）In, ultrasonication processing power is 200~1000W, and the time is >=15min.
7. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 2）In, immersion total time is 5 ~ 48h, blots number >=2 time.
8. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 2）In, freeze-dryer is -25 ~ -60 DEG C, and sublimation drying is 10 ~ 48h.
9. the preparation method of carbonization bacteria cellulose/carbon nanotube membrane material according to claim 1, which is characterized in that
Step 3）In, Carbonization Conditions are 300 ~ 500 DEG C, and constant temperature time is 0.5 ~ 5h.
10. the preparation method of claim 1-9 any one of them carbonization bacteria cellulose/multi-walled carbon nanotube membrane material is obtained
Carbonization bacteria cellulose/multi-walled carbon nanotube the membrane material obtained.
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| CN110739462B (en) * | 2019-10-16 | 2022-05-24 | 南京林业大学 | Flexible carbon film substrate material and preparation method and application thereof |
| CN112746087A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Method for detoxifying lignocellulose hydrolysate |
| CN112746087B (en) * | 2019-10-31 | 2023-01-10 | 中国石油化工股份有限公司 | Method for detoxifying lignocellulose hydrolysate |
| CN110642590B (en) * | 2019-11-01 | 2022-02-01 | 江苏集萃先进高分子材料研究所有限公司 | Preparation method of super-hydrophobic and high-absorption electromagnetic shielding cellulose-based composite carbon aerogel |
| CN110642590A (en) * | 2019-11-01 | 2020-01-03 | 江苏集萃先进高分子材料研究所有限公司 | Preparation method of super-hydrophobic and high-absorption electromagnetic shielding cellulose-based composite carbon aerogel |
| CN111785531A (en) * | 2020-06-12 | 2020-10-16 | 杭州电子科技大学 | Preparation method of carbon nanotube/bacterial cellulose aerogel material and super capacitor |
| CN112072093A (en) * | 2020-09-18 | 2020-12-11 | 天科新能源有限责任公司 | Lithium battery negative electrode slurry with good dispersion effect and preparation method thereof |
| CN112707566A (en) * | 2020-12-24 | 2021-04-27 | 中国矿业大学 | Functionalized carbon-based salt difference power generation permeable membrane and preparation method and application thereof |
| CN112876744A (en) * | 2021-01-15 | 2021-06-01 | 湖南大学 | Method for enhancing mechanical property of nano cellulose membrane by using lignosulfonate |
| CN113113592A (en) * | 2021-03-24 | 2021-07-13 | 杭州电子科技大学 | Preparation method of sulfur/carbon nanotube/carbon nanofiber composite electrode material |
| CN113113592B (en) * | 2021-03-24 | 2022-05-06 | 杭州电子科技大学 | Preparation method of sulfur/carbon nanotube/carbon nanofiber composite electrode material |
| GB2611330A (en) * | 2021-09-30 | 2023-04-05 | Univ Limerick | Carbon foam materials |
| CN114941240A (en) * | 2022-05-16 | 2022-08-26 | 电子科技大学长三角研究院(湖州) | Preparation method of water-resistant carbon nanotube aerogel composite fiber electrode |
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