CN104591118A - Preparation method of three-dimensional type graphene/carbon nano-tube composite bead - Google Patents

Preparation method of three-dimensional type graphene/carbon nano-tube composite bead Download PDF

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CN104591118A
CN104591118A CN201510001489.9A CN201510001489A CN104591118A CN 104591118 A CN104591118 A CN 104591118A CN 201510001489 A CN201510001489 A CN 201510001489A CN 104591118 A CN104591118 A CN 104591118A
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carbon nano
graphene
temperature
tube
preparation
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CN104591118B (en
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孙立国
曹晓俭
张艳红
汪成
赵冬梅
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Heilongjiang University
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Heilongjiang University
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Abstract

The invention discloses a preparation method of a three-dimensional type graphene/carbon nano-tube composite bead, relates to a preparation method of a three-dimensional type graphene/carbon nano-tube composite bead and aims at solving the problems in the prior art of complex operation, difficulty in post-processing and large grain size dispersibility in the process of preparing a three-dimensional graphene/carbon nano-tube composite. The preparation method comprises the following steps: mixing a graphene oxide liquid and a carbon nano-tube after acid treatment, and carrying out ultrasonic treatment to prepare a dispersion phase liquid; with dimethicone as a mobile phase, obtaining monodispersed droplets by virtue of an injection pump, and then collecting the droplets into a vessel made of a polypropylene material; and curing the droplets in a drying box at the temperature of 60 DEG C, putting into a muffle furnace, and calcining to obtain the three-dimensional type graphene/carbon nano-tube composite bead. The preparation method is used for preparing the three-dimensional type graphene/carbon nano-tube composite bead.

Description

A kind of preparation method of three-dimensional shape graphene/carbon nano-tube compounded microbeads
Technical field
The present invention relates to a kind of preparation method of three-dimensional shape graphene/carbon nano-tube compounded microbeads.
Background technology
Graphene, has the two-dirnentional structure of monoatomic layer thickness, has large theoretical specific surface area, high electronic conductivity, good chemical stability and lower production cost.Since it is obtained by mechanically peel by Geim first, due to the characteristic of its uniqueness, is extensively studied in catalysis, Energy conversion, storage and sensor and has applied.Carbon nanotube is then a kind of One-dimensional Quantum material with special construction, the cylinder that flake graphite alkene is rolled into can be regarded in theory as, there is unique hollow structure, nano-scale, abnormal high aspect ratio and larger specific surface area, have single wall and many walls point.From it since 1991 are found by Iijima, due to its outstanding physical and chemical performance, mechanical characteristics and thermostability, make it at numerous areas as electronics, solar cell, catalysis, environmental area and biotechnology industry etc. have various application.Graphene/carbon nanotube composite material combines the two advantage, by the synergistic effect between them, makes it show the performance more excellent than any one single-material, as isotropy heat conductance, electrochemical capacitance etc.Based on this, Graphene/carbon nanotube composite material has broad application prospects in ultracapacitor, indicating meter, biological detection etc.
Three-dimensional Graphene/carbon nanotube composite material, as a kind of novel aggregated structure, has caused the extensive concern of scientific circles.By in-situ chemical vapour phase reduction sedimentation, Chen etc. prepare the Graphene/carbon nanotube composite material of tridimensional network; By the phase-change method of gentleness, Xiaowei Ma etc. prepares three-dimensional flower shape β-Ni (OH) 2/ GO/CNTs matrix material; By the method that in-situ chemical reduces, Yang etc. select ethylene glycol to make reductive agent, reduce the graphene/carbon nano-tube compound aqueous solution of different ratios under ice-water bath condition, obtain the Graphene/carbon nanotube composite material with hierarchy after drying after filtration.Laifa Shen etc. use liquid phase method to synthesize three-dimensional TiO 2-GNS-CNT nano composite material, makes ultra-fine TiO 2nanocrystal growth is in the Graphene of two dimension and the carbon nano tube surface of one dimension, and this material can be used for the preparation of lithium cell; Du etc., by inserting the carbon nanotube of growth of vertical arrangement in the orderly pyrolytic graphite of pyrolysis phthalocyanine dyestuffs thermotropism expansion height, prepare adjustable three-dimensional column Graphene/carbon nanotube structure; Seok-Hu Bae etc. pass through microblogging self assembly 3D graphene-carbon nano tube-nickel nanostructure, can be used as high-capacity cathode material in lithium ion battery; Alfred T.Chidembo etc. obtain the isotropic graphene-carbon nano tube-nickel oxide ternary structural of self-assembly with spray heating decomposition, wherein contain part spherical structure.In the prior art, there is the problem such as preparation process complexity, aftertreatment difficulty in the preparation of three-dimensional structure graphene/carbon nano-tube, especially in preparation graphene/carbon nano-tube complex microsphere, does not give prominence to obtain simple effective method mostly.
Summary of the invention
The present invention will solve prior art preparing three-dimensional grapheme/carbon nano tube compound material to occur complicated operation in process, aftertreatment difficulty, problem that Particle dispersity is larger, and provides a kind of preparation method of three-dimensional shape graphene/carbon nano-tube compounded microbeads.
The preparation method of a kind of three-dimensional shape graphene/carbon nano-tube of the present invention compounded microbeads carries out according to the following steps:
One, carbon nanotube is placed in nitration mixture, back flow reaction 2h ~ 3h under temperature is 80 DEG C ~ 85 DEG C conditions, carries out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 60 DEG C ~ 70 DEG C carries out drying, obtains the carbon nanotube powder after processing;
The quality of described carbon nanotube and the volume ratio of nitration mixture are 1:(90 ~ 100); Described nitration mixture is concentrated nitric acid with the vitriol oil is 1:(2 ~ 4 by volume) mixture that mixes, wherein the massfraction of the vitriol oil is 98%, and the massfraction of concentrated nitric acid is 65%;
Two, the carbon nanotube powder after process step one obtained mixes with graphene oxide water solution, and low whipping speed is 300r/min ~ 400r/min and ultrasonic frequency is process 5h ~ 10h under the condition of 40KHz ~ 50KHz, obtains disperse phase solution; The solid content of described graphene oxide water solution is 1% ~ 1.5%;
Carbon nanotube powder after the process that described step one obtains and the mass ratio of graphene oxide water solution are 1:(0.01 ~ 0.5);
Three, disperse phase solution step 2 obtained is poured in No. 1 syringe, dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the disperse phase solution in No. 1 syringe and No. 2 syringes, obtain graphene/carbon nano-tube compounded microbeads to be oxidized;
Described No. 1 syringe and No. 2 injector to inject pump outlet are connected to one end of same PTFE tube; The other end of described PTFE tube is connected with PP material receptor;
The volume ratio of the disperse phase solution in described No. 1 syringe and the dimethyl silicone oil in No. 2 syringes is 1:(5 ~ 20);
The propelling speed of described No. 1 syringe is 0.5:(110 ~ 130 with the ratio of the propelling speed of No. 2 syringes);
Four, it is that the loft drier of 60 DEG C ~ 70 DEG C solidifies 12h ~ 24h that the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in temperature, then n-hexane is used 4 ~ 6 times, being placed in baking oven again adopts substep intensification heating method to carry out oven dry preoxidation, obtains graphene/carbon nano-tube compounded microbeads after preoxidation;
Described employing substep intensification heating method carries out drying preoxidation process: being dry preoxidation 6h ~ 9h under the condition of 140 DEG C ~ 160 DEG C in temperature, is then dry preoxidation 1.5h ~ 2h under the condition of 270 DEG C ~ 290 DEG C in temperature;
Five, under nitrogen atmosphere, after the preoxidation obtain step 4, graphene/carbon nano-tube compounded microbeads carries out carbonizing treatment, obtains three-dimensional shape graphene/carbon nano-tube compounded microbeads;
Described carbonizing treatment process is: be 700 DEG C ~ 800 DEG C with the temperature rise rate of 4 DEG C/min ~ 6 DEG C/min by room temperature to temperature, and is incubated 1.5h ~ 2.5h at temperature is 700 DEG C ~ 800 DEG C.
Beneficial effect of the present invention:
Acid-treated carbon nanotube is mixed the disperse phase solution obtaining having certain viscosity through supersound process by the present invention with graphene oxide water solution, pass through micro fluidic device, using dimethyl silicone oil as moving phase, mixing solutions prepares graphene/carbon nano-tube compounded microbeads as disperse phase, again microballon is cured and preoxidation, after calcination processing, finally obtain three-dimensional shape graphene/carbon nano-tube compounded microbeads.The method is novel unique, simple to operate, and aftertreatment is easy, and process safety is reliably environmentally friendly, and the bead size obtained is controlled, uniform particle diameter, pattern are peculiar.That carbon material those skilled in the art prepare three-dimensional grapheme/carbon nanotube compounded microbeads one method more easily.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the carbon nanotube powder after the process that obtains of step one;
The SEM that Fig. 2 is graphene oxide water solution described in step 2 schemes;
Fig. 3 is 100 times of SEM figure of three-dimensional shape graphene/carbon nano-tube compounded microbeads;
Fig. 4 is 40000 times of SEM figure of three-dimensional shape graphene/carbon nano-tube compounded microbeads;
Fig. 5 is 40000 times of SEM figure of three-dimensional shape graphene/carbon nano-tube compounded microbeads inside.
Embodiment
Embodiment one: the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube of present embodiment compounded microbeads carries out according to the following steps:
One, carbon nanotube is placed in nitration mixture, back flow reaction 2h ~ 3h under temperature is 80 DEG C ~ 85 DEG C conditions, carries out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 60 DEG C ~ 70 DEG C carries out drying, obtains the carbon nanotube powder after processing;
The quality of described carbon nanotube and the volume ratio of nitration mixture are 1:(90 ~ 100); Described nitration mixture is concentrated nitric acid with the vitriol oil is 1:(2 ~ 4 by volume) mixture that mixes, wherein the massfraction of the vitriol oil is 98%, and the massfraction of concentrated nitric acid is 65%;
Two, the carbon nanotube powder after process step one obtained mixes with graphene oxide water solution, and low whipping speed is 300r/min ~ 400r/min and ultrasonic frequency is process 5h ~ 10h under the condition of 40KHz ~ 50KHz, obtains disperse phase solution; The solid content of described graphene oxide water solution is 1% ~ 1.5%;
Carbon nanotube powder after the process that described step one obtains and the mass ratio of graphene oxide water solution are 1:(0.01 ~ 0.5);
Three, disperse phase solution step 2 obtained is poured in No. 1 syringe, dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the disperse phase solution in No. 1 syringe and No. 2 syringes, obtain graphene/carbon nano-tube compounded microbeads to be oxidized;
Described No. 1 syringe and No. 2 injector to inject pump outlet are connected to one end of same PTFE tube; The other end of described PTFE tube is connected with PP material receptor;
The volume ratio of the disperse phase solution in described No. 1 syringe and the dimethyl silicone oil in No. 2 syringes is 1:(5 ~ 20);
The propelling speed of described No. 1 syringe is 0.5:(110 ~ 130 with the ratio of the propelling speed of No. 2 syringes);
Four, it is that the loft drier of 60 DEG C ~ 70 DEG C solidifies 12h ~ 24h that the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in temperature, then n-hexane is used 4 ~ 6 times, being placed in baking oven again adopts substep intensification heating method to carry out oven dry preoxidation, obtains graphene/carbon nano-tube compounded microbeads after preoxidation;
Described employing substep intensification heating method carries out drying preoxidation process: being dry preoxidation 6h ~ 9h under the condition of 140 DEG C ~ 160 DEG C in temperature, is then dry preoxidation 1.5h ~ 2h under the condition of 270 DEG C ~ 290 DEG C in temperature;
Five, under nitrogen atmosphere, after the preoxidation obtain step 4, graphene/carbon nano-tube compounded microbeads carries out carbonizing treatment, obtains three-dimensional shape graphene/carbon nano-tube compounded microbeads;
Described carbonizing treatment process is: be 700 DEG C ~ 800 DEG C with the temperature rise rate of 4 DEG C/min ~ 6 DEG C/min by room temperature to temperature, and is incubated 1.5h ~ 2.5h at temperature is 700 DEG C ~ 800 DEG C.
Embodiment two: present embodiment and embodiment one are concentrated nitric acid with the vitriol oil unlike: nitration mixture described in step one is mixture that 1:3 mixes by volume.Other are identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the carbon nanotube powder after the process that step one described in step 2 obtains and the mass ratio of graphene oxide water solution are 1:0.1.Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are 1:10 unlike the volume ratio of the dimethyl silicone oil in: the disperse phase solution in No. 1 syringe described in step 3 and No. 2 syringes.Other are identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the propelling speed of No. 1 syringe described in step 3 is 0.5:120 with the ratio of the propelling speed of No. 2 syringes.Other are identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: loft drier described in step 4 is air dry oven or vacuum drying oven.Other are identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: adopt substep intensification heating method to carry out drying preoxidation process and be described in step 4: being dry preoxidation 9h under the condition of 150 DEG C in temperature, is then dry preoxidation 2h under the condition of 280 DEG C in temperature.Other are identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the carbonizing treatment process described in step 5 is: be 750 DEG C with the temperature rise rate of 5 DEG C/min by room temperature to temperature, and is incubated 2h at temperature is 750 DEG C.Other are identical with one of embodiment one to seven.
Effect of the present invention is verified by following examples:
Embodiment one: a kind of preparation method of three-dimensional shape graphene/carbon nano-tube compounded microbeads carries out according to the following steps:
One, carbon nanotube is placed in nitration mixture, back flow reaction 3h under temperature is 80 DEG C of conditions, carries out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 70 DEG C carries out drying, obtains the carbon nanotube powder after processing;
The massfraction of the described nitration mixture mixture that to be concentrated nitric acid mix for 1:3 by volume with the vitriol oil wherein vitriol oil is 98%, and the massfraction of concentrated nitric acid is 65%;
Two, the carbon nanotube powder after process 0.1g step one obtained mixes with 0.05g graphene oxide water solution, low whipping speed is 300r/min ~ 400r/min and ultrasonic frequency is process 5h ~ 10h under the condition of 40KHz ~ 50KHz, obtains disperse phase solution; The solid content of described graphene oxide water solution is 1%;
Three, the disperse phase solution that 10mL step 2 obtains is poured in No. 1 syringe, 50mL dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the disperse phase solution in No. 1 syringe and No. 2 syringes, obtain graphene/carbon nano-tube compounded microbeads to be oxidized;
Described No. 1 syringe and No. 2 injector to inject pump outlet are connected to one end of same PTFE tube; The other end of described PTFE tube is connected with PP material receptor;
The propelling speed of described No. 1 syringe is 0.5:120 with the ratio of the propelling speed of No. 2 syringes;
Four, it is that the loft drier of 60 DEG C solidifies 24h that the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in temperature, then n-hexane is used 6 times, being placed in baking oven again adopts substep intensification heating method to carry out oven dry preoxidation, obtains graphene/carbon nano-tube compounded microbeads after preoxidation;
Described employing substep intensification heating method is dried preoxidation process and is: being dry preoxidation 9h under the condition of 150 DEG C in temperature, is then dry preoxidation 2h under the condition of 280 DEG C in temperature;
Five, under nitrogen atmosphere, after the preoxidation obtain step 4, graphene/carbon nano-tube compounded microbeads carries out carbonizing treatment, obtains three-dimensional shape graphene/carbon nano-tube compounded microbeads;
Described carbonizing treatment process is: be 750 DEG C with the temperature rise rate of 5 DEG C/min by room temperature to temperature, and is incubated 2h at temperature is 750 DEG C.
Fig. 1 is the SEM figure of the carbon nanotube powder after the process that obtains of step one; The tubular structure of carbon nanotube and a large amount of carbon nanotube are wound around mutually as we can see from the figure;
The SEM that Fig. 2 is graphene oxide water solution described in step 2 schemes; As can be seen from the figure very thin specific to Graphene lamella fold pattern;
Fig. 3 is 100 times of SEM figure of three-dimensional shape graphene/carbon nano-tube compounded microbeads; As can be seen from the figure the peculiar pattern of the three-dimensional of complex microsphere, has rough, wrinkled surface, and also have the existence of tubular structure, particle diameter is relatively homogeneous, at about 150nm simultaneously.
Fig. 4 is 40000 times of SEM figure of three-dimensional shape graphene/carbon nano-tube compounded microbeads; Demonstrate the fold pattern of graphene sheet layer and the tubular structure of carbon nanotube in figure, in a large amount of fold lamella, be interspersed with carbon nanotube.
Fig. 5 is 40000 times of SEM figure of three-dimensional shape graphene/carbon nano-tube compounded microbeads inside; The SEM figure of compounded microbeads inside demonstrates a large amount of carbon nanotube be mutually wound around and is present in graphene film interlayer, shows that the graphene sheet layer of two dimension and the carbon nanotube compound of one dimension obtain the Graphene/carbon nanotube composite material of three-dimensional structure.

Claims (8)

1. a preparation method for three-dimensional shape graphene/carbon nano-tube compounded microbeads, is characterized in that the preparation method of three-dimensional shape graphene/carbon nano-tube compounded microbeads carries out according to the following steps:
One, carbon nanotube is placed in nitration mixture, back flow reaction 2h ~ 3h under temperature is 80 DEG C ~ 85 DEG C conditions, carries out dialysis after centrifuge washing, then to be placed in temperature be that the baking oven of 60 DEG C ~ 70 DEG C carries out drying, obtains the carbon nanotube powder after processing;
The quality of described carbon nanotube and the volume ratio of nitration mixture are 1:(90 ~ 100); Described nitration mixture is concentrated nitric acid with the vitriol oil is 1:(2 ~ 4 by volume) mixture that mixes, wherein the massfraction of the vitriol oil is 98%, and the massfraction of concentrated nitric acid is 65%;
Two, the carbon nanotube powder after process step one obtained mixes with graphene oxide water solution, and low whipping speed is 300r/min ~ 400r/min and ultrasonic frequency is process 5h ~ 10h under the condition of 40KHz ~ 50KHz, obtains disperse phase solution; The solid content of described graphene oxide water solution is 1% ~ 1.5%;
Carbon nanotube powder after the process that described step one obtains and the mass ratio of graphene oxide water solution are 1:(0.01 ~ 0.5);
Three, disperse phase solution step 2 obtained is poured in No. 1 syringe, dimethyl silicone oil is poured in No. 2 syringes, use syringe pump to be advanced in PP material receptor by the dimethyl silicone oil in the disperse phase solution in No. 1 syringe and No. 2 syringes, obtain graphene/carbon nano-tube compounded microbeads to be oxidized;
Described No. 1 syringe and No. 2 injector to inject pump outlet are connected to one end of same PTFE tube; The other end of described PTFE tube is connected with PP material receptor;
The volume ratio of the disperse phase solution in described No. 1 syringe and the dimethyl silicone oil in No. 2 syringes is 1:(5 ~ 20);
The propelling speed of described No. 1 syringe is 0.5:(110 ~ 130 with the ratio of the propelling speed of No. 2 syringes);
Four, it is that the loft drier of 60 DEG C ~ 70 DEG C solidifies 12h ~ 24h that the graphene/carbon nano-tube compounded microbeads to be oxidized step 3 obtained is placed in temperature, then n-hexane is used 4 ~ 6 times, being placed in baking oven again adopts substep intensification heating method to carry out oven dry preoxidation, obtains graphene/carbon nano-tube compounded microbeads after preoxidation;
Described employing substep intensification heating method carries out drying preoxidation process: being dry preoxidation 6h ~ 9h under the condition of 140 DEG C ~ 160 DEG C in temperature, is then dry preoxidation 1.5h ~ 2h under the condition of 270 DEG C ~ 290 DEG C in temperature;
Five, under nitrogen atmosphere, after the preoxidation obtain step 4, graphene/carbon nano-tube compounded microbeads carries out carbonizing treatment, obtains three-dimensional shape graphene/carbon nano-tube compounded microbeads;
Described carbonizing treatment process is: be 700 DEG C ~ 800 DEG C with the temperature rise rate of 4 DEG C/min ~ 6 DEG C/min by room temperature to temperature, and is incubated 1.5h ~ 2.5h at temperature is 700 DEG C ~ 800 DEG C.
2. the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads according to claim 1, is characterized in that nitration mixture described in step one be concentrated nitric acid with the vitriol oil is mixture that 1:3 mixes by volume.
3. the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads according to claim 1, is characterized in that the mass ratio of the carbon nanotube powder after the process that step one described in step 2 obtains and graphene oxide water solution is 1:0.1.
4. the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads according to claim 1, is characterized in that the volume ratio of the disperse phase solution in No. 1 syringe described in step 3 and the dimethyl silicone oil in No. 2 syringes is 1:10.
5. the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads according to claim 1, is characterized in that the propelling speed of No. 1 syringe described in step 3 is 0.5:120 with the ratio of the propelling speed of No. 2 syringes.
6. the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads according to claim 1, is characterized in that loft drier described in step 4 is air dry oven or vacuum drying oven.
7. the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads according to claim 1, it is characterized in that adopting substep intensification heating method to carry out oven dry preoxidation process described in step 4 is: being dry preoxidation 9h under the condition of 150 DEG C in temperature, is then dry preoxidation 2h under the condition of 280 DEG C in temperature.
8. the preparation method of a kind of three-dimensional shape graphene/carbon nano-tube compounded microbeads according to claim 1, it is characterized in that the carbonizing treatment process described in step 5 is: be 750 DEG C with the temperature rise rate of 5 DEG C/min by room temperature to temperature, and be incubated 2h at temperature is 750 DEG C.
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CN109830382A (en) * 2019-04-01 2019-05-31 黑龙江东方学院 A kind of preparation method and application of the graphene/carbon nano-tube compounded microbeads with core-shell structure
CN110465317A (en) * 2018-10-18 2019-11-19 黑龙江大学 A kind of photochemical catalyst g-C3N4/ GO/ magnetic particle and preparation method thereof
CN111204741A (en) * 2020-01-15 2020-05-29 北京科技大学 Preparation method of three-dimensional graphene/carbon nanotube cross-linked composite material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108091878A (en) * 2017-12-05 2018-05-29 四川华昆能源有限责任公司 A kind of preparation method of lithium-sulfur cell graphene carbon nanotube composite conducting skeleton
CN108091878B (en) * 2017-12-05 2020-06-09 四川华昆能源有限责任公司 Preparation method of graphene carbon nanotube composite conductive framework for lithium-sulfur battery
CN110465317A (en) * 2018-10-18 2019-11-19 黑龙江大学 A kind of photochemical catalyst g-C3N4/ GO/ magnetic particle and preparation method thereof
CN109830382A (en) * 2019-04-01 2019-05-31 黑龙江东方学院 A kind of preparation method and application of the graphene/carbon nano-tube compounded microbeads with core-shell structure
CN111204741A (en) * 2020-01-15 2020-05-29 北京科技大学 Preparation method of three-dimensional graphene/carbon nanotube cross-linked composite material

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