CN115340740B - Integrated carbon nanotube grafted graphene conductive composite material, preparation method thereof and application thereof in elastic current collector - Google Patents
Integrated carbon nanotube grafted graphene conductive composite material, preparation method thereof and application thereof in elastic current collector Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 56
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 5
- 229920000307 polymer substrate Polymers 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical group [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- C—CHEMISTRY; METALLURGY
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- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0862—Nickel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to an integrated carbon nanotube grafted graphene conductive composite material, a preparation method thereof and application thereof in an elastic current collector, and belongs to the technical field of flexible electrode materials. The invention discloses an integrated carbon nano tube grafted graphene conductive composite material (CNT-g-Gr), which is of a three-dimensional network structure, and is connected with graphene and carbon nano tubes by taking Ni metal nano particles as nodes. The invention also discloses a conductive elastomer, which comprises an elastic polymer substrate, wherein the inside of the conductive elastomer contains the carbon nano tube grafted graphene conductive composite material.
Description
Technical Field
The invention belongs to the technical field of flexible electrode materials, and relates to an integrated carbon nanotube grafted graphene conductive composite material, a preparation method thereof and application thereof in an elastic current collector.
Background
In the current society, intelligent wearable and integrated electronic products rapidly develop, and the intelligent wearable and integrated electronic products directly penetrate into important fields such as medical treatment and health, sports health, information entertainment and the like related to the life quality of people. Emerging flexible smart wearable electronic devices place higher demands on the flexibility and stretchability of the micro-battery. In order to ensure that the wearable equipment can be suitable for different deformation scenes, the stretchability of the energy storage device is important. However, conventional flexible batteries that are flexible and foldable have a tensile set of less than 10%, and in many wearable devices attached to the skin, muscles, especially joints of the human body, and integrated into stretchable fabrics, the tensile set is greater than 50%. In wearable flexible batteries, the design and preparation of flexible and stretchable current collectors is one of the most important parts, however, most of the current collectors suffer from structural failure, breakage of internal conductive networks and shedding of active materials from the current collectors under mechanical stress. To meet the energy and deformation requirements of flexible wearable electronics, the current collector must have excellent energy density and stretchability.
The current collector is a component forming the core of the battery, and the main function is to collect the current generated in the charging and discharging process of the battery active material and then output the current to the outside, which is important to the performance of the battery. Conventional current collectors (aluminum foil, copper foil, etc.) are no longer suitable for use in stretchable battery systems. In order to maintain the stability of electrochemical performance of the electrode in a stretched state, it is important to ensure that the current collector still has excellent conductivity under synchronous deformation. The introduction of the novel elastic material fundamentally changes the structure of the electrode and the current collector in the traditional battery. The stretchable conductive elastomer is prepared by compounding conductive filler and elastic material, wherein the most widely used filler is still graphite, graphene, carbon nano tube and the like. However, due to the ultrahigh length-diameter ratio and specific surface area of the carbon nanotubes and the graphene, extremely strong van der Waals force exists between single carbon nanotubes and between single-layer and few-layer graphene, aggregation and entanglement are extremely easy to occur, the formation of a conductive network inside a polymer is affected, and in a state that the battery is stretched and greatly deformed, the internal conductive network structure of an elastic current collector taking the graphene or the carbon nanotubes as a conductive filler is subjected to disconnection and fracture, so that conductivity reduction is caused, the electrochemical performance of the battery is seriously affected, and the wearable equipment cannot normally operate.
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides an integrated carbon nano tube grafted graphene conductive composite material with a three-dimensional network structure.
The aim of the invention can be achieved by the following technical scheme:
an integrated carbon nano tube grafted graphene conductive composite material (CNT-g-Gr), wherein the integrated carbon nano tube grafted graphene conductive composite material is of a three-dimensional network structure, and Ni metal nano particles are used as nodes to connect graphene and carbon nano tubes.
According to the invention, graphene and carbon nanotubes with ultrahigh conductivity are connected by taking Ni metal nano particles with ultrahigh conductivity as nodes, and the structure endows the material with ultrahigh conductivity.
Preferably, the specific surface area of the integrated carbon nanotube grafted graphene conductive composite material is 1000-2500m 2/g.
The invention also discloses a preparation method of the integrated carbon nanotube grafted graphene conductive composite material, which comprises the following steps: mixing glucose monohydrate, ammonium chloride and divalent nickel inorganic acid salt with deionized water, drying, grinding to obtain mixed powder, adding the mixed powder into a binary salt system consisting of sodium chloride and potassium chloride, preheating, transferring the preheated material into a tubular furnace, preserving heat in an argon atmosphere, switching to an acetylene gas channel, continuing preserving heat, switching to an argon gas channel, cooling to normal temperature, cleaning, and drying to obtain the carbon nanotube grafted graphene conductive composite material.
The invention adopts a simple and easy-to-operate, low-cost and environment-friendly molten salt method, and in the ionic flux of the KCl/NaCl eutectic salt at high temperature, the ionic liquid environment with strong polarity is favorable for converting sp 3 hybridized C-C or C-X into sp 2 hybridized C-C, and glucose is directly converted into graphene materials. In the molten salt method, the conversion process of glucose into graphene is carried out, and the lone pair electrons doped on the N atoms on the aromatic ring small molecule fragments can form conjugated structures with pi bonds in the carbocycle, so that the aromatic ring fragments with a large number of sp 2 hybridized carbons can be recombined to form graphene. Meanwhile, in a high-temperature strong-polarity ionic liquid environment, a cracking gas with reducibility is generated when glucose is converted into graphene, divalent nickel ions in a precursor can be reduced into metallic nickel, and Ni nano particles (Ni@Gr) are generated on the surface of the graphene in situ. On the basis of Ni@Gr, the environment of high Wen Jixing ionic liquid is directly maintained so as to promote the graphene sheet layer of the Ni@Gr to be in a stretching state, acetylene gas is introduced, the Carbon Nano Tube (CNT) is more efficiently grown by taking Ni nano particles as catalytic sites, and the generated carbon nano tube is used as a bracket to effectively prop open the graphene sheet layer (Gr), so that the CNT-g-Gr conductive composite material with an integrated three-dimensional network structure and an ultrahigh specific surface area is prepared.
Preferably, the mass ratio of the glucose monohydrate to the ammonium chloride to the divalent nickel inorganic acid salt is 100: (30-100): (2-15).
Further preferably, the mass ratio of the mixed powder of the glucose monohydrate, the ammonium chloride and the divalent nickel inorganic acid salt to the deionized water is 1: (0.5-1.5).
Still more preferably, the divalent nickel mineral acid salt is one or more of nickel chloride and nickel nitrate.
Preferably, the mass ratio of sodium chloride to potassium chloride in the binary salt system is 1: (0.5-1.5).
Preferably, the mass ratio of the glucose monohydrate to the binary salt system is 1: (10-100).
Further preferably, the mass ratio of the mixed powder to the binary salt system is 1: (20-100).
Preferably, the preheating temperature is 100-200 ℃ and the time is 5-24h.
In the preheating treatment stage, glucose monohydrate and ammonium chloride undergo Maillard reaction to generate a graphene precursor.
Preferably, the temperature kept in the argon atmosphere is a first temperature, and the heat-preserving time is a first heat-preserving time; the temperature of the heat preservation in the acetylene gas is the second temperature, and the heat preservation time is the second heat preservation time.
Further preferably, the first temperature is higher than the second temperature; wherein the first temperature is 800-1300 ℃, and the second temperature is 750-1000 ℃.
Further preferably, the first holding time is 30-120min, and the second holding time is 5-60min.
Preferably, the heating rate in the tube furnace is 5-30 ℃/min.
The invention also discloses a conductive elastomer, which comprises an elastic polymer substrate, wherein the inside of the conductive elastomer contains the carbon nano tube grafted graphene conductive composite material.
Preferably, the conductive elastomer is prepared from a carbon nanotube grafted graphene conductive composite material, a surfactant and a polymer emulsion.
According to the invention, the conductive elastomer with ultrahigh conductivity is prepared from the carbon nanotube grafted graphene conductive composite material serving as a raw material, so that the ultrahigh conductivity of the conductive elastomer is endowed, and meanwhile, the good deformability and stretchability of the conductive elastomer are endowed, so that the prepared elastic current collector can still keep a good internal conductive network structure and conductivity in a stretched state.
Preferably, the thickness of the conductive elastomer is 50 μm to 150 μm.
Further preferably, the polymer comprises one or more of polystyrene-ethylene-butylene-styrene, polystyrene-polymethyl acrylate-polystyrene, polystyrene-poly-n-butyl acrylate-polystyrene, polyimide, polyvinylidene fluoride, polytetrafluoroethylene, polydimethylsiloxane.
Preferably, the surfactant is sodium dodecyl sulfonate.
Preferably, the preparation method of the conductive elastomer comprises the following steps: and (3) dropwise adding the polymer emulsion into a dispersion liquid composed of the carbon nanotube grafted graphene conductive composite material, a surfactant and deionized water, then placing the prepared mixed liquid into a polytetrafluoroethylene surface dish for film forming, and cleaning and annealing to obtain the conductive elastomer.
Further preferably, the carbon nanotube grafted graphene conductive composite is prepared into a solution with the concentration of 5-15mg/mL with deionized water.
Preferably, the mass ratio of the carbon nanotube grafted graphene conductive composite material to the surfactant in the dispersion liquid is 1: (1-10).
Further preferably, the dispersion is prepared by magnetic stirring and ultrasonic treatment in sequence.
Preferably, the solid content of the carbon nanotube grafted graphene conductive composite material in the mixed solution is 1-15wt%.
Further preferably, the solid content of the carbon nanotube grafted graphene conductive composite in the mixed solution is 5-10wt%.
Preferably, the film forming temperature is 30 to 60 ℃.
Preferably, the annealing temperature is 25-70 ℃, the time is 10-48h, and the vacuum degree is-0.08 Mpa.
Compared with the prior art, the invention has the following beneficial effects:
1. The integrated carbon nanotube grafted graphene conductive composite material has a three-dimensional network structure, and the graphene and the carbon nanotubes are connected by taking the Ni metal nanoparticles as nodes, so that the connection is more stable and has slidability, and under the condition that the graphene conductive material is dispersed in a stretching state, the graphene conductive material can still be mutually communicated through the carbon nanotubes, and the conductivity stability of the conductive elastomer in the stretching state can be further ensured.
2. The process raw material has low cost, the preparation process is simple, the generation of strong acid waste liquid in the traditional graphene preparation process by using the oxidation-reduction method is avoided, and the prepared CNT-g-Gr conductive composite material with the integrated three-dimensional network structure has excellent conductivity by adopting a chemical vapor deposition method.
3. According to the invention, a simple and easy-to-operate low-cost and environment-friendly molten salt method is adopted, in the ionic flux of high-temperature KCl/NaCl eutectic salt, the ionic liquid environment with strong polarity is favorable for converting sp 3 hybridized C-C or C-X into sp 2 hybridized C-C, glucose is directly converted into graphene materials, meanwhile, a cracking gas with reducibility is generated, divalent nickel ions in the precursor can be reduced into metallic nickel, and Ni nano particles (Ni@Gr) are generated on the surface of graphene in situ.
4. In the conductive elastomer formed by blending the integrated carbon nanotube grafted graphene conductive composite material serving as the conductive filler and the polymer, a stable conductive network structure can be formed, and a benzene ring on the adopted polymer can generate strong pi-pi conjugated interaction with a large number of delocalized covalent bonds on the surfaces of CNTs and Gr, so that the dispersion of CNT-g-Gr in a polymer matrix is facilitated, and the conductivity of a current collector is greatly improved; compared with conventional conductive fillers such as Ag nano-sheets/nano-wires, carbon nano-tubes, graphene and the like, the conductive filler has more stable conductivity in a stretching state.
5. The conductive elastomer has excellent elasticity and conductivity, and has very wide application prospects in stretchable electrodes and flexible wearable equipment.
Drawings
Fig. 1 is a TEM image of an integrated carbon nanotube-grafted graphene conductive composite material prepared in example 1 of the present invention.
Fig. 2 is an X-ray diffraction analysis chart of the integrated carbon nanotube-grafted graphene conductive composite material prepared in example 1 of the present invention.
Fig. 3 is a schematic diagram of an integrated carbon nanotube-grafted graphene conductive composite material prepared in example 1 of the present invention.
Fig. 4 is a schematic diagram showing the change of the internal conductive network structure of the conductive elastomer prepared in example 1 of the present invention when stretching.
Description of the drawings: 1. carbon nano tube, 2, metallic nickel nano particles, 3, graphene, 4, CNT-g-Gr composite material, 5, graphene sheet layer, 6, elastic polymer substrate.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1
Weighing 1.98g of glucose, 0.35g of nickel nitrate and 1.51g of ammonium chloride, grinding uniformly in a mortar, adding equal mass of deionized water, stirring uniformly, drying in the shade, then placing in a vacuum drying oven at 60 ℃ for continuous drying for 12 hours, transferring the obtained mixed powder into the mortar, and grinding uniformly to obtain mixed powder. Then, 53.6g of potassium chloride and 45.6g of sodium chloride are weighed and added into an agate ball milling tank together, the ball milling speed is 300rpm, and the binary salt system is obtained after grinding for 1 hour. After ball milling, the materials in the first two steps are mechanically stirred in a mortar, and are transferred into a square quartz boat after being uniformly mixed, and are preheated for 8 hours at a constant temperature of 100 ℃ in a blast drier. Then transferring the mixture into a tube furnace, quickly heating to a first temperature of 1000 ℃ at 5 ℃/min in an argon atmosphere, preserving heat for 60min, stopping heating, naturally cooling to 950 ℃, switching to an acetylene gas channel, restarting heating, performing constant temperature treatment for 30min at a second temperature of 950 ℃, stopping heating, switching to an argon gas channel again, and protecting the argon gas atmosphere in the whole cooling process until the temperature is reduced to normal temperature. And taking out the product, washing with deionized water for 5 times to remove salt, and carrying out vacuum annealing treatment at 80 ℃ for 24 hours to obtain the integrated carbon nanotube grafted graphene conductive composite material (CNT-g-Gr), wherein a TEM image of the integrated carbon nanotube grafted graphene conductive composite material is shown in figure 1. Fig. 2 is an X-ray diffraction analysis chart of the composite material, and three peaks after 20 ° correspond to 002 crystal face of CNT, 111 crystal face of metallic Ni, and 200 crystal face of metallic Ni in order.
Taking 16.5mg of the prepared integrated carbon nanotube grafted graphene conductive composite material (CNT-g-Gr) and 50mg of sodium dodecyl benzene sulfonate, taking 10mL of deionized water, magnetically stirring, performing ultrasonic treatment at 300W power for 30min to prepare CNT-g-Gr dispersion, slowly and dropwise adding polystyrene-poly-n-butyl acrylate-polystyrene emulsion into the CNT-g-Gr dispersion, and magnetically stirring for 15min to complete the blending, wherein the solid content of the CNT-g-Gr in the conductive elastomer is 5 wt%. Covering the mixed solution into a polytetrafluoroethylene surface dish, forming a film at 50 ℃, placing the film into a Buchner funnel after the film forming is finished, repeatedly filtering and washing with deionized water, removing a surfactant in the film, placing the falling film into a vacuum oven at 70 ℃ for 10 hours after the washing is finished, annealing, and eliminating internal stress to obtain the composite conductive elastomer of polystyrene-polymethyl acrylate-polystyrene and CNT-g-Gr. FIG. 3 is a schematic diagram of the resulting integrated carbon nanotube-grafted graphene conductive composite; fig. 4 is a schematic diagram showing the structural change of an internal conductive network of the prepared conductive elastomer when the conductive elastomer is stretched, and it can be observed that graphene sheets in the carbon nanotube grafted graphene conductive composite material are grafted with carbon nanotubes; and the carbon nanotubes are stretched, but are always connected with the graphene grafted conductive composite material. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 5.72S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 5.09S/cm, and the retention rate is 88.99%.
Example 2
The difference compared to example 1 is that the polymer is a polystyrene-ethylene-butylene-styrene emulsion. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 4.56S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 3.87S/cm, and the retention rate is 84.87%.
Example 3
The difference compared to example 1 is that the first temperature is 800℃and the second temperature is 750 ℃. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 4.39S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 3.70S/cm, and the retention rate is 84.28%.
Example 4
The difference compared to example 1 is that the first temperature is 1300℃and the second temperature is 1000 ℃. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 4.30S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 3.47S/cm, and the retention rate is 80.70%.
Example 5
The difference compared to example 1 is that the first temperature and the second temperature are the same, both being 900 ℃. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 4.13S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 3.01S/cm, and the retention rate is 72.88%.
Example 6
The difference compared to example 1 is that the first temperature is 780℃and the second temperature is 700 ℃. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 3.90S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 2.75S/cm, and the retention rate is 70.51%.
Example 7
The difference compared to example 1 is that the first temperature is 800℃and the second temperature is 700 ℃. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 3.85S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 2.72S/cm, and the retention rate is 70.65%.
Example 8
The difference compared to example 1 is that the first temperature is 1350 deg.c and the second temperature is 700 deg.c. And characterizing the volume resistivity of the current collector under different stretching states by adopting a four-probe resistivity tester, and calculating the conductivity of the current collector under different stretching states. When not stretched, the conductivity of the current collector is 3.35S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 2.30S/cm, and the retention rate is 68.66%.
Comparative example 1
Weighing 1.98g of glucose and 1.51g of ammonium chloride, grinding uniformly in a mortar, adding deionized water with equal mass, stirring uniformly, drying in the shade, then placing in a vacuum drying oven at 60 ℃ for continuous drying for 12 hours, transferring the obtained solidified product into the mortar, grinding uniformly, and standing by. Then, 53.6g of potassium chloride and 45.6g of sodium chloride are weighed and added into an agate ball milling tank, the ball milling speed is 300rpm, and the ball milling is carried out for 2 hours. After ball milling, the materials in the first two steps are mechanically stirred in a mortar, transferred into a square quartz boat after being uniformly mixed, and pretreated for 8 hours at the constant temperature of 100 ℃ in a blast drier. Transferring into a tube furnace, quickly heating to 800 ℃ at 5 ℃/min, treating for 60min, stopping heating, naturally cooling, and protecting in the whole argon atmosphere. And taking out the product, repeatedly washing with deionized water to remove salt, carrying out suction filtration, and carrying out vacuum drying at 80 ℃ for 24 hours to obtain the nitrogen-doped graphene material.
Then, a composite conductive elastomer is prepared according to the method in the embodiment 1, the volume resistivity of the current collector under different stretching states is characterized by adopting a four-probe resistivity tester, and the conductivity of the current collector under different stretching states is calculated. When not stretched, the conductivity of the current collector is 3.16S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 1.29S/cm, and the retention rate is 40.82%.
Comparative example 2
Weighing 1.98g of glucose, 0.22g of nickel chloride and 1.51g of ammonium chloride, grinding uniformly in a mortar, adding equal mass of deionized water, stirring uniformly, drying in the shade, then placing in a vacuum drying oven at 60 ℃ for continuous drying for 12 hours, transferring the obtained solidified product into the mortar, grinding uniformly, and standing for later use. Then, 53.6g of potassium chloride and 45.6g of sodium chloride are weighed and added into an agate ball milling tank together, and the ball milling speed is 300rpm, and the mixture is milled for 1 hour. After ball milling, the materials in the first two steps are mechanically stirred in a mortar, transferred into a square quartz boat after being uniformly mixed, and pretreated for 8 hours at the constant temperature of 100 ℃ in a blast drier. Transferring into a tube furnace, quickly heating to 900 ℃ at 5 ℃/min, treating for 60min, stopping heating, naturally cooling, and protecting in the whole argon atmosphere. And taking out the product, repeatedly washing with deionized water to remove salt, and vacuum drying at 80 ℃ for 24 hours to obtain the graphene and metallic nickel nanoparticle composite material.
Then, a composite conductive elastomer is prepared according to the method in the embodiment 1, the volume resistivity of the current collector under different stretching states is characterized by adopting a four-probe resistivity tester, and the conductivity of the current collector under different stretching states is calculated. When not stretched, the conductivity of the current collector is 2.63S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 0.76S/cm, and the retention rate is 28.89%.
Comparative example 3
1.98G of glucose, 53.6g of potassium chloride and 45.6g of sodium chloride are weighed together into an agate ball milling pot, and the ball milling speed is 200rpm, and the grinding is carried out for 1h. After ball milling, the materials are tiled into square quartz boats, and are pretreated for 5 hours at a constant temperature of 100 ℃ in a blast drier. Transferring into a tube furnace, quickly heating to 800 ℃ at 5 ℃/min, treating for 20min, stopping heating, naturally cooling, and protecting in the whole argon atmosphere. And taking out the product, repeatedly washing with deionized water to remove salt, and vacuum drying at 80 ℃ for 24 hours to obtain the graphene material.
Then, a composite conductive elastomer is prepared according to the method in the embodiment 1, the volume resistivity of the current collector under different stretching states is characterized by adopting a four-probe resistivity tester, and the conductivity of the current collector under different stretching states is calculated. When not stretched, the conductivity of the current collector is 2.14S/cm; when the tensile deformation reaches 50%, the conductivity of the current collector is 0.87S/cm, and the retention rate is 40.65%.
The graphene contained in comparative examples 1 to 3 still had a certain conductivity, but the conductivity stability in the stretched state was rapidly lowered due to the absence of carbon nanotube connection.
In conclusion, the integrated carbon nanotube grafted graphene conductive composite material has a three-dimensional network structure and has good conductivity; and the conductive elastomer prepared from the conductive composite material can be applied in the flexible intelligent wearable field, and people keep good stability under the stretching condition.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (15)
1. The conductive elastomer is characterized by comprising an elastic polymer substrate, wherein an integrated carbon nano tube grafted graphene conductive composite material is contained in the elastic polymer substrate;
the conductive elastomer is prepared from an integrated carbon nano tube grafted graphene conductive composite material, a surfactant and a polymer emulsion;
the polymer emulsion comprises one or more of polystyrene-ethylene-butylene-styrene, polystyrene-polymethyl acrylate-polystyrene, polystyrene-poly-n-butyl acrylate-polystyrene;
The preparation method of the conductive elastomer comprises the following steps: dropwise adding the polymer emulsion into a dispersion liquid composed of an integrated carbon nanotube grafted graphene conductive composite material, a surfactant and deionized water, then placing the prepared mixed liquid into a polytetrafluoroethylene surface dish to form a film, and cleaning and annealing to obtain a conductive elastomer;
the integrated carbon nano tube grafted graphene conductive composite material is of a three-dimensional network structure, and graphene and carbon nano tubes are connected by taking Ni metal nano particles as nodes;
the preparation method of the integrated carbon nanotube grafted graphene conductive composite material comprises the following steps: mixing glucose monohydrate, ammonium chloride and divalent nickel inorganic acid salt with deionized water, drying, grinding to obtain mixed powder, adding the mixed powder into a binary salt system consisting of sodium chloride and potassium chloride, preheating, transferring the preheated material into a tubular furnace, preserving heat in an argon atmosphere, switching to an acetylene gas channel, continuing preserving heat, switching to an argon gas channel, cooling to normal temperature, cleaning, and drying to obtain the integrated carbon nanotube grafted graphene conductive composite material.
2. The conductive elastomer of claim 1, wherein the conductive elastomer has a thickness of 50 μm to 150 μm.
3. The conductive elastomer of claim 1, wherein the integrated carbon nanotube grafted graphene conductive composite has a specific surface area of 1000-2500 m 2/g.
4. The conductive elastomer according to claim 1, wherein the mass ratio of the glucose monohydrate, the ammonium chloride and the divalent nickel mineral acid salt is 100: (30-100): (2-15).
5. The conductive elastomer according to claim 1, wherein the mass ratio of the mixed powder to the binary salt system is 1: (20-100).
6. The conductive elastomer according to claim 1, wherein the temperature kept in the argon atmosphere is a first temperature and the keeping time is a first keeping time; the temperature of the heat preservation in the acetylene gas is the second temperature, and the heat preservation time is the second heat preservation time.
7. The conductive elastomer of claim 6, wherein the first temperature is higher than the second temperature.
8. A method of preparing the conductive elastomer of claim 1, comprising: and (3) dropwise adding the polymer emulsion into a dispersion liquid composed of an integrated carbon nanotube grafted graphene conductive composite material, a surfactant and deionized water, then placing the prepared mixed liquid into a polytetrafluoroethylene surface dish to form a film, and cleaning and annealing to obtain the conductive elastomer.
9. The preparation method of claim 8, wherein the mass ratio of the integrated carbon nanotube grafted graphene conductive composite material to the surfactant in the dispersion is 1: (1-10).
10. The preparation method of claim 8, wherein the solid content of the integrated carbon nanotube-grafted graphene conductive composite in the mixed solution is 1-15wt%.
11. The method according to claim 8, wherein the annealing temperature is 25 ℃ to 70 ℃, the time is 10 to 48 hours, and the vacuum degree is-0.08 Mpa.
12. The preparation method according to claim 8, wherein the mass ratio of the glucose monohydrate, the ammonium chloride and the divalent nickel mineral acid salt is 100: (30-100): (2-15).
13. The preparation method according to claim 8, wherein the mass ratio of the mixed powder to the binary salt system is 1: (20-100).
14. The method according to claim 8, wherein the temperature kept in the argon atmosphere is a first temperature and the keeping time is a first keeping time; the temperature of the heat preservation in the acetylene gas is the second temperature, and the heat preservation time is the second heat preservation time.
15. The method of claim 14, wherein the first temperature is higher than the second temperature.
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