CN106629690A - Method for reinforcing three-dimensional graphene porous material structure - Google Patents
Method for reinforcing three-dimensional graphene porous material structure Download PDFInfo
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- CN106629690A CN106629690A CN201610876765.0A CN201610876765A CN106629690A CN 106629690 A CN106629690 A CN 106629690A CN 201610876765 A CN201610876765 A CN 201610876765A CN 106629690 A CN106629690 A CN 106629690A
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- porous material
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
A method for reinforcing a three-dimensional graphene porous material structure includes the specific steps: treating three-dimensional graphene porous materials prepared by a wet process in a microwave plasma deposition system; depositing carbon materials on material surfaces and inner walls of pores by the aid of plasma technology; reinforcing a three-dimensional graphene skeleton structure to achieve good bridging functions among graphene sheet layers on the inner walls of the pores. Internal defects of three-dimensional graphene porous materials caused by the wet process are remedied, and graphene sheets are seamlessly connected to form a compact communicated network structure and obtain high-performance porous materials with high mechanical strength, good electrical conductivity and stable thermal property.
Description
Technical field
The present invention relates to nano material, belonging to three-dimensional grapheme porous material strengthens technical field, specially a kind of reinforcement
The method of three-dimensional grapheme porous material structure.
Background technology
Graphene is carbon atom with sp2The two dimensional crystal structure that hybridized orbit is formed by connecting, its perfect carbon crystal structure
Impart the special physicochemical characteristics of Graphene：Remarkable mechanical performance, excellent conduction, heat conductivility etc..In recent years, state
Two-dimensional graphene piece is assembled into three-dimensional grapheme porous material by inside and outside researcher, and this porous material shows ultralow
The features such as density, high porosity and higher specific surface area.For traditional material, three-dimensional grapheme porous material
Strengthen, be electromagnetically shielded and biological medicine in energy storage and conversion, active electrode material, sensor, environmental improvement, composite
There is huge application potential and development space Deng field.
Different according to raw material original state, preparing the method for three-dimensional grapheme porous material can be divided into dry and wet.It is dry
Method is usually to utilize chemical vapour deposition technique, and with hydrocarbon gas as carbon source, Jing Pintsch process is separated out into carbon atom in matrix
Core promotes Graphene growth in situ, and graphene film is covalently connected to become a complete network structure, therefore shows
Go out the performance of superelevation.But investment of this method to equipment is very big, and energy resource consumption is more, realize that large-scale production still has pole
Big challenge.Wet method covers with graphene oxide solution all methods that three-dimensional grapheme porous material is prepared as raw material, bag
Include hydro-thermal method, electronation self-assembly method, sol-gel process and template etc..This method has low production cost, prepares simply
And it is practical the features such as, be conducive to being mass produced.But in three-dimensional grapheme porous material prepared by wet method, stone
Black alkene piece defect is more and is susceptible to reunite, it is difficult to forms good overlap joint, causes three-dimensional grapheme porous material each side
Performance falls flat.
The content of the invention
In order to make up many defects of the three-dimensional grapheme porous material of wet method preparation, need to carry out reinforcement solutions to it.
For this problem, a kind of method of utilization microwave plasma reinforcement body three-dimensional grapheme porous material structure is we have proposed.
Three-dimensional grapheme porous material prepared by wet method is placed in microwave plasma system and is processed, existed using plasma technique
Material surface and inwall depositing carbon material, reinforcement three-dimensional graphene framework structure, this method makes its hole graphite on inner wall alkene piece
Good bridge joint effect is formed between layer, the three-dimensional grapheme porous material internal flaw of wet method preparation is made up so that Graphene
Piece is seamlessly connected, and constitutes the network of a fine and close connection, maintains the integrality of three-dimensional structure, obtains a kind of high mechanical strength, leads
The stable high-performance porous material of good electrical property, thermal property.
To achieve these goals, the technical scheme taken：A kind of side of reinforcement three-dimensional grapheme porous material structure
Method, comprises the following steps：
First, it is immersed in catalyst solution after the three-dimensional grapheme porous material carbonization treatment for preparing wet method, standing 2～
12h, then takes out drying by three-dimensional grapheme porous material.
Described carburizing temperature is 200～1000 DEG C, and carbonization atmosphere is the inert gases such as nitrogen, argon gas, helium.
Described catalyst is selected from metallic salts with catalytic such as ferric nitrate, nickel nitrate, cobalt nitrates.
Described dry run is：30～200 DEG C of temperature, the time is 1～12h.
2nd, the three-dimensional grapheme porous material containing catalyst is placed in microwave plasma system, using plasma
Body technique, in certain pressure intensity and auxiliary atmosphere, adjusts the catalysis adhered on power activation three-dimensional grapheme porous material
Agent, keeps constant pressure, and under certain power, is passed through carbon-source gas, on the top layer of three-dimensional grapheme porous material and interior
Wall depositing carbon material, obtains the fine and close connection Graphene porous material of three-dimensional of reinforcement solutions.
In the microwave plasma deposition system：The power of activated catalyst is 50～400W, produces plasma source
Pressure be 100～1000Pa, power be 50～800W, the sedimentation time of material with carbon element is 1～30min.
The one kind of the auxiliary gas of described Plasma deposition systems in the gases such as hydrogen, argon gas, nitrogen, helium
Or it is several, gas flux is 9～150sccm, is passed through the time for 5～60min.
The carbon-source gas of described Plasma deposition systems selected from methane, ethane, propane, butane, pentane, acetylene, third
In the gases such as alkynes, butine, ethene, propylene, butylene one or more, gas flux is 3～100sccm, be passed through the time for 1～
40min。
The carbon source and auxiliary gas flux ratio being passed through in described Plasma deposition systems is 1: 2～1: 30.
Specific embodiment
A kind of method of the present invention is provided reinforcement three-dimensional grapheme porous material structure with reference to specific embodiment
It is described in detail.
Embodiment 1：
(1) 200 DEG C of carbonizations in the tube furnace that three-dimensional grapheme porous material made by hydro-thermal method is put under nitrogen atmosphere
Process 2h.4g nickel nitrates are dissolved in 48g ethanol by 1: 12 mass ratio, are stirred to nickel nitrate and is completely dissolved, then by carbon
Three-dimensional grapheme porous material more stable after change is immersed in 5h in above-mentioned solution and takes out, and dries in vacuum drying oven.
(2) quartz chamber body for the three-dimensional grapheme porous material containing nickel nitrate being placed on into microwave plasma system is true
In empty room so that three-dimensional grapheme porous material is fully placed oneself in the midst of in plasma atmosphere, and then regulating system pressure is extremely
200Pa, is then passed through continual and steady hydrogen by 39.5sccm, opens plasma source, adjusts power to 200W, activating catalytic
Agent；Keep pressure, power, hydrogen constant, be passed through methane gas by 13.5sccm so that material with carbon element is more in three-dimensional grapheme
Sedimentation time in Porous materials is 3min.Then it is taken out from cavity and 3h is cooled down in vacuum environment, that is, obtained top layer
With the three-dimensional fine and close connected porous material of inwall depositing carbon material.
Embodiment 2：
(1) 400 DEG C in the tube furnace that three-dimensional grapheme porous material made by sol-gel process is put under nitrogen atmosphere
Carbonization treatment 2h.6g ferric nitrates are dissolved in 36ml deionized waters by 1: 6 mass ratio, are stirred to ferric nitrate and is completely dissolved, so
Afterwards three-dimensional grapheme porous material more stable after carbonization is immersed in into 7h in above-mentioned solution to take out, is dried in vacuum drying oven.
(2) quartz chamber body for the three-dimensional grapheme porous material containing ferric nitrate being placed on into microwave plasma system is true
In empty room so that three-dimensional grapheme porous material is fully placed oneself in the midst of in plasma atmosphere, then vacuumize in cavity, then adjust
Then section system pressure each leads into argon gas, hydrogen, holding chamber while being passed through gas to 300Pa by 16sccm and 20sccm
In vivo pressure is constant, adjusts power and causes activation of catalyst to 300W, and pressure, power are then kept after catalyst system is formed
It is constant, it is passed through methane gas by 12sccm so that sedimentation time of the material with carbon element in three-dimensional grapheme porous material is 10min.
Then take out from cavity and 4h is cooled down in vacuum environment, that is, obtained top layer and connected with the three-dimensional densification of inwall depositing carbon material
Porous material.
Embodiment 3：
(1) three-dimensional grapheme porous material made by Chemical assembly method is placed on 500 DEG C in the tube furnace under argon atmosphere
Carbonization treatment 3h.4g cobalt nitrates are dissolved in 32ml deionized waters by 1: 8 mass ratio, are stirred to cobalt nitrate and is completely dissolved, so
Afterwards the three-dimensional grapheme porous material being heat-treated is immersed in into 5h in above-mentioned solution to take out, is dried in vacuum drying oven.
(2) the three-dimensional grapheme porous material containing cobalt nitrate is placed on the quartz chamber body vacuum of microwave plasma system
It is indoor so that three-dimensional grapheme porous material is fully placed oneself in the midst of in plasma atmosphere, is then shut off valve, take out true in cavity
It is empty.Then then regulating system pressure be passed through continual and steady hydrogen to 200Pa by 36.5sccm, opens plasma source, adjusts
Section power 400W makes activation of catalyst, maintains pressure, power constant after catalyst system is formed, and by 13.5sccm air-flow is passed through
Stable methane gas, makes sedimentation time of the material with carbon element in three-dimensional grapheme porous material be 15min.Then by it from cavity
Interior taking-up cools down 6h in vacuum environment, that is, obtained the three-dimensional fine and close connected porous material of top layer and inwall depositing carbon material.
Claims (9)
1. a kind of method of reinforcement three-dimensional grapheme porous material structure, it is characterised in that：Using plasma technique in wet method
Made by three-dimensional grapheme porous material top layer and hole inwall depositing carbon material, reinforcement three-dimensional graphene framework structure so that
Good bridge joint effect is formed between graphene sheet layer, and then constitutes the network structure of fine and close connection.
2. a kind of method of the reinforcement three-dimensional grapheme porous material structure described in claim 1, comprises the following steps：
(1) it is immersed in catalyst solution after the three-dimensional grapheme porous material carbonization treatment for preparing wet method, stands 2～12h,
Then three-dimensional grapheme porous material is taken out into drying.
(2) the three-dimensional grapheme porous material containing catalyst is placed in microwave plasma system, using plasma skill
Art, in certain pressure intensity and auxiliary atmosphere, adjusts the catalyst adhered on power activation three-dimensional grapheme porous material, protects
Constant pressure is held, and under certain power, is passed through carbon-source gas, deposited on the top layer of three-dimensional grapheme porous material and inwall
Material with carbon element, obtains the fine and close connection Graphene porous material of three-dimensional of reinforcement solutions.
3. the method for a kind of reinforcement three-dimensional grapheme porous material structure according to claim 2, it is characterised in that：Step
(1) carburizing temperature is 200～1000 DEG C in, and carbonization atmosphere is the inert gases such as nitrogen, argon gas, helium.
4. the method for a kind of reinforcement three-dimensional grapheme porous material structure according to claim 2, it is characterised in that：Step
(1) catalyst includes the metallic salts with catalytic such as ferric nitrate, nickel nitrate, cobalt nitrate in.
5. the method for a kind of reinforcement three-dimensional grapheme porous material structure according to claim 2, it is characterised in that：Step
(2) dry run is in：30～200 DEG C of temperature, the time is 1～12h.
6. the method for a kind of reinforcement three-dimensional grapheme porous material structure according to claim 2, it is characterised in that：Step
(2) in microwave plasma deposition system：The power of activated catalyst is 50～400W, and the pressure for producing plasma source is
100～1000Pa, power are 50～800W, and the sedimentation time of material with carbon element is 1～30min.
7. the method for a kind of reinforcement three-dimensional grapheme porous material structure according to claim 2, it is characterised in that：Step
(2) auxiliary gas includes one or more in the gas such as hydrogen, argon gas, nitrogen, helium in, gas flux is 9～
150sccm, is passed through the time for 5～60min.
8. the method for a kind of reinforcement three-dimensional grapheme porous material structure according to claim 2, it is characterised in that：Step
(2) carbon source is in the gases such as methane, ethane, propane, butane, pentane, acetylene, propine, butine, ethene, propylene, butylene in
Plant or several, gas flux is 3～100sccm, be passed through the time for 1～40min.
9. the method for a kind of reinforcement three-dimensional grapheme porous material structure according to claim 2, it is characterised in that：Step
(2) flux ratio of carbon source and auxiliary gas is 1: 2～1: 30 in.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130527A (en) * | 2017-05-19 | 2017-09-05 | 山东交通职业学院 | A kind of use graphene film reinforces the construction method of T-shaped beam |
| CN108358191A (en) * | 2018-05-10 | 2018-08-03 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of low defect graphene and preparation method thereof |
| CN108658065A (en) * | 2018-08-22 | 2018-10-16 | 恒力（厦门）石墨烯科技产业集团有限公司 | A kind of doping of graphene prepares and restorative procedure |
| CN108862252A (en) * | 2018-07-06 | 2018-11-23 | 中国科学院上海微***与信息技术研究所 | A method of doped graphene is prepared using ion implanting |
| CN110316725A (en) * | 2019-07-23 | 2019-10-11 | 浙江大学 | A kind of high-density high-strength graphene frame material and preparation method thereof |
| CN111099917A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Porous composite material for generating electric arc in microwave and preparation method thereof |
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| CN105236384A (en) * | 2015-09-25 | 2016-01-13 | 天津工业大学 | Method for preparing three dimensional graphene/carbon nanotube ultra-light structure |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107130527A (en) * | 2017-05-19 | 2017-09-05 | 山东交通职业学院 | A kind of use graphene film reinforces the construction method of T-shaped beam |
| CN108358191A (en) * | 2018-05-10 | 2018-08-03 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of low defect graphene and preparation method thereof |
| CN108358191B (en) * | 2018-05-10 | 2022-04-29 | 郑州新世纪材料基因组工程研究院有限公司 | Low-defect graphene and preparation method thereof |
| CN108862252A (en) * | 2018-07-06 | 2018-11-23 | 中国科学院上海微***与信息技术研究所 | A method of doped graphene is prepared using ion implanting |
| CN108658065A (en) * | 2018-08-22 | 2018-10-16 | 恒力（厦门）石墨烯科技产业集团有限公司 | A kind of doping of graphene prepares and restorative procedure |
| CN111099917A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Porous composite material for generating electric arc in microwave and preparation method thereof |
| CN111099917B (en) * | 2018-10-29 | 2022-01-04 | 中国石油化工股份有限公司 | Porous composite material for generating electric arc in microwave and preparation method thereof |
| CN110316725A (en) * | 2019-07-23 | 2019-10-11 | 浙江大学 | A kind of high-density high-strength graphene frame material and preparation method thereof |
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Application publication date: 20170510 |