CN116377714A - Composite graphene non-woven fabric, preparation method and application thereof - Google Patents
Composite graphene non-woven fabric, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
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- 239000010949 copper Substances 0.000 claims abstract description 34
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- 238000000034 method Methods 0.000 claims description 15
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention discloses a composite graphene non-woven fabric, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, uniformly dispersing graphene oxide fibers in an aqueous solvent, and then filtering and depositing through a filter screen to obtain graphene oxide fiber non-woven fabrics on the filter screen; s2, thermally annealing the graphene oxide fiber non-woven fabric obtained in the step S1 to obtain graphene fiber non-woven fabric; and S3, immersing the graphene fiber non-woven fabric obtained in the step S2 in an electrolytic copper plating solution to perform electroless copper plating, and then cleaning and drying to obtain the graphene fiber non-woven fabric. By adopting the scheme, the high-conductivity non-woven fabric formed by the Cu cladding on the fiber is obtained, has low density, excellent thermal conductivity, electric conductivity and electromagnetic shielding performance, and also has excellent mechanical strength and flexibility, and has great application prospect in the aspects of preparing lightning stroke protection, and heat transfer and conductive elements of radiators or other structures in electronic equipment.
Description
Technical Field
The invention relates to a graphene composite material, in particular to a composite graphene non-woven fabric, a preparation method and application thereof.
Background
Graphene is an allotrope of carbon having only a single atomic layer thickness, has the highest strength, high thermal conductivity, and carrier mobility among known materials, and thus attracts great attention. The graphene fiber is an assembled structure of a two-dimensional graphene sheet layer under a one-dimensional macroscopic scale, and has higher strength and extremely high electric conduction, heat conduction and other performances. The macroscopic material benefits from the excellent properties of graphene, and therefore has great potential and value.
One of the strategies for pushing the graphene fibers to further go to practical application is to weave the graphene fibers to obtain a functional fabric with certain flexibility, high electric conductivity and high heat conductivity. Carbon-based fabrics are popular in many fields of energy, automotive, aerospace, and the like because of their advantages in combining electrical and thermal conductivity, flame and chemical resistance, permeability, and lightweight properties. However, carbon-based fabrics have a general problem in that it is still challenging to achieve strong inter-fiber interactions due to the fire resistance and insolubility of the carbon material, and thus the performance of the fabric may be significantly reduced compared to single fibers, particularly for electrical and thermal conductivity sensitive to interfacial resistance, resulting in a limited range of use of the fabric.
Disclosure of Invention
Aiming at the problem that the conductivity and the thermal conductivity of the graphene fiber fabric are reduced compared with those of single fibers, the invention provides a composite graphene non-woven fabric, a preparation method and application thereof.
In order to achieve the above purpose, the present invention provides a method for preparing a composite graphene nonwoven fabric, the method comprising the following steps:
s1, uniformly dispersing graphene oxide fibers in an aqueous solvent, and then filtering and depositing through a filter screen to obtain graphene oxide fiber non-woven fabrics on the filter screen;
s2, thermally annealing the graphene oxide fiber non-woven fabric obtained in the step S1 to obtain graphene fiber non-woven fabric;
and S3, immersing the graphene fiber non-woven fabric obtained in the step S2 in an electrolytic copper plating solution to perform electroless copper plating, and then cleaning and drying to obtain the graphene fiber non-woven fabric.
The graphene nonwoven fabric prepared in step S2 uses an extensible strategy to produce a randomly laid nonwoven fabric GFF constructed from graphene staple fibers. The individual fibers are integrated into the entire fabric with strong inter-fiber bonding by wet-melt assembly of Graphene Oxide (GO) fibers in an aqueous solvent. After annealing, the molten GFFs were found to be tough, pliable, lightweight and highly conductive. Their specific electrical and thermal conductivity is several times higher than previous carbon-based papers/fabrics, even for single graphene fibers.
By adopting the scheme of the invention, the high-conductivity non-woven fabric consisting of the Cu cladding on the fiber is obtained, and the density is low (can reach 0.42 g cm -3 ) The in-plane conductivity reaches 1.78X10 6 S m -1 The heat conductivity coefficient reaches 1.65X10 3 W m -1 K -1 The composite material has high thermal conductivity, excellent electrical conductivity, excellent mechanical strength and flexibility, and has great application prospect in preparing lightning strike protection, and heat-transfer and conductive elements of radiators or other structures in electronic equipment.
After the GFF copper plating, a remarkable effect is exerted in the electromagnetic shielding process. This highly conductive porous fibrous network architecture with the proper thickness, as a way to reduce the density of shielding materials and increase multiple internal reflections, is the beginning of high EMI shielding. In general, the total EMI Shielding Effect (SET) is the sum of all attenuation functions, including reflection (SER), absorption (standard error) one) and multiple internal reflections (SEM). It is speculated that the proposed function of the EMI shielding mechanism in cu@gff is further understood. When an incident electromagnetic wave (EMW) hits the cu@gff surface, the surface reflection is minimal and most of the wave enters the fabric interior through sufficient voids. Metallic materials are high performance EMI candidates because of the conductive loss and multiple charge carriers that can be generated by the highly conductive surfaces. In this process, the incident wave is immediately and continuously re-reflected or partially absorbed or dissipated in the limited three-dimensional space of any stacked fiber barriers. In addition, reflected waves reaching many individual fibers can be further attenuated by multiple internal reflections on a microscopic scale, mainly due to the multi-interface geometry of the fiber surface cladding (microscopic coalescence induced reflective layer and some voids). Finally, the multiple internal reflection effects at both the microscopic and macroscopic levels attenuate the remaining electromagnetic waves, leaving negligible EMW.
Specifically, in step S1, the preparation method of the graphene oxide fiber includes:
s1.1, dispersing graphene oxide in N, N-Dimethylformamide (DMF) to prepare spinning solution, wherein the mass volume ratio of the graphene oxide to the N, N-dimethylformamide is 1: (3-5);
s1.2, adjusting the injection and rotation speed ratio 1: and (140-420), enabling the spinning solution to enter ethyl acetate coagulating liquid to be coagulated into filaments, and obtaining the graphene oxide fibers.
Specifically, in step S1, the aqueous solvent includes a volume ratio of (1-3): 1 water and ethanol.
Specifically, in step S2, the temperature of the thermal annealing is 1000-3500 ℃ and the time is 2h. The inter-melted GO fiber fabric (GOFF) generated in the step S1 can be further converted into GFF through thermal annealing at 1000-3500 ℃.
Specifically, in step S3, the copper solution includes the following components in mass ratio (23-25): 4: copper sulfate pentahydrate (90-93), formaldehyde solution and disodium ethylenediamine tetraacetate dihydrate, and the pH is 12.0-12.5.
Specifically, in the step S3, copper plating is performed at 40-50 ℃ for 1-10 minutes.
According to the invention, based on an electroless copper plating method, a thin copper layer uniformly covered on the surface of the fiber is deposited through electroless plating, so that the performance of the functional component with high electric conductivity and heat conduction is greatly improved.
Preferably, the following pretreatment is further performed before copper plating the graphene fiber nonwoven fabric obtained in step S2: immersing the non-woven fabric in a molar concentration ratio of 1:1, in the mixed solution of tin chloride and hydrochloric acid for 0.5-1 h, cleaning and drying, and immersing in a molar concentration ratio of 7:1250 and hydrochloric acid for 0.5 to 1 hour, and then cleaning and drying.
The second aspect of the invention provides a composite graphene non-woven fabric prepared by the preparation method.
The third aspect of the invention provides an application of the composite graphene non-woven fabric in preparing lightning stroke protection, a radiator in electronic equipment or a heat transfer conductive element.
Through the technical scheme, the invention has the following beneficial effects:
1. according to the invention, a thin copper layer uniformly covered on the surface of the fiber is deposited on the graphene non-woven fabric by an electroless copper plating method to serve as a high-conductivity functional component. The thermal conductivity and the electric conductivity of the copper-plated graphene composite non-woven fabric are respectively 1.65X10 3 Wm -1 K -1 And 1.78X10 6 S m -1 . Compared with the non-copper-plated graphene non-woven fabric, the thermal conductivity and the electrical conductivity of the non-copper-plated graphene non-woven fabric are obviously improved after copper plating, and the composite graphene non-woven fabric prepared by the method has obvious advantages in light weight, electrical conductivity and thermal conductivity improvement rate.
Drawings
FIG. 1 is a macroscopic view of the GFF nonwoven fabric prepared in example 1 of the present invention;
FIG. 2 is a macroscopic view of the composite graphene nonwoven fabric prepared in example 1 of the present invention;
fig. 3 is a microstructure view of the composite graphene nonwoven fabric prepared in example 1 of the present invention.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to examples. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
Example 1
(1) Dispersing graphene oxide in DMF (the mass volume ratio of the graphene oxide to the DMF is 1:5) to prepare spinning solution, injecting the GO/DMF spinning solution into ethyl acetate coagulation bath with the rotation speed of 40r.p.m, and adjusting the speed ratio of injection to rotation to be 1:140, the rotary coagulation tank applies excessive stretching to the extruded fiber by friction force and generates a short GO fiber of a specific length;
(2) The spun GO fibers were collected by filtration and dried at 60 ℃. Redispersing the dried fibers in H 2 O and ethanol (volume ratio is 3:1), then filtering and depositing through a filter screen, and then drying to produce a intersoluble GO fiber non-woven fabric (GOFF);
(3) Thermal annealing at 1000 ℃ further converts the GOFF to a GFF nonwoven, as shown in fig. 1;
(4) Soaking GFF in deionized water for 12 hours, and then washing to eliminate impurities on the surface of the fiber; sensitization of GFF for 0.5h using 100ml of a mixed solution of 0.1M tin chloride and 0.1M hydrochloric acid; subsequently, after GFF was scrubbed with distilled water and dried again, the fabric was immersed in 100ml of a mixture of 0.0014M palladium chloride and 0.25M hydrochloric acid for 0.5 hours to perform an activation reaction, and a washing and drying process was further performed before final plating;
(5) Preparing a Cu solution for electroplating: 5g of copper sulfate pentahydrate, 0.8g of formaldehyde solution and 18.6g of ethylenediamine tetraacetic acid disodium salt dihydrate are dissolved in 98 mL deionized water, and then the pH of the Cu solution is controlled to be 12.2-12.5 by adding a proper amount of NaOH solution;
(6) Immersing the GFF nonwoven fabric treated in the step (4) in a copper solution bath at a temperature of 40 ℃ for 1min, washing and drying, and collecting an electroless copper plating GFF product, namely a composite graphene nonwoven fabric, which shows a relatively smooth surface due to a high surface area, has less impurities and a porous structure, the porous surface is favorable for catalytic sites on the fibers, and further accelerates deposition of Cu on the fiber surface, as shown in fig. 2 to 3. At the beginning of electroplating, cu nanoparticles or nanoclusters are incorporated into the fiber surface and the entire fiber is partially encapsulated. The dense cladding of Cu has the effect of prolonged electroless plating time and a fully covered metal layer is observed. Since many metal particles are anchored or piled up through the pores to embed into the surface, the Cu coating firmly wraps the fiber surface, which means that the prepared Cu-coated graphene fiber nonwoven composite has building stability, practicality and durability.
Example 2
(1) Dispersing graphene oxide in DMF (the mass volume ratio of the graphene oxide to the DMF is 1:3) to prepare spinning solution, injecting the GO/DMF spinning solution into ethyl acetate coagulation bath with the rotation speed of 40r.p.m, and adjusting the speed ratio of injection to rotation to be 1:420, the rotary coagulation tank applies excessive stretching to the extruded fiber by friction force and generates a short GO fiber of a specific length;
(2) The spun GO fibers were collected by filtration and dried at 60 ℃. Redispersing the dried fibers in H 2 O and ethanol (volume ratio is 1:1), then filtering and depositing through a filter screen, and then drying to produce a intersoluble GO fiber non-woven fabric (GOFF);
(3) Further converting the GOFF into GFF nonwoven fabrics by thermal annealing at 3500 ℃;
(4) Soaking GFF in deionized water for 12 hours, and then washing to eliminate impurities on the surface of the fiber; sensitization of GFF for 1h using 100ml of a mixed solution of 0.1M tin chloride and 0.1M hydrochloric acid; subsequently, after GFF was scrubbed with distilled water and dried again, the fabric was immersed in 100ml of a mixture of 0.0014M palladium chloride and 0.25M hydrochloric acid for 1 hour to perform an activation reaction, and a washing and drying process was further performed before final plating;
(5) Preparing a Cu solution for electroplating: 5g of copper sulfate pentahydrate, 0.8g of formaldehyde solution and 18.6g of ethylenediamine tetraacetic acid disodium salt dihydrate are dissolved in 98 mL deionized water, and then the pH of the Cu solution is controlled to be 12.2-12.5 by adding a proper amount of NaOH solution;
(6) Immersing the GFF non-woven fabric treated in the step (4) into a copper solution bath for 10min at the temperature of 50 ℃, washing and drying, and collecting an electroless copper-plated GFF product, namely the composite graphene non-woven fabric.
Example 3
Other conditions were the same as in example 1, except that step (4) was omitted.
Examples 4 to 6
Other conditions were the same as in example 1, except that the plating time was respectively modified to 3min, 5min, and 10min.
Example 7
Other conditions are the same as in example 2 except that step (4) is omitted.
Comparative example 1
Other conditions were the same as in example 1 except that steps (4) - (6) were omitted.
Comparative example 2
Other conditions were the same as in example 1, except that steps (1) - (3) were replaced with films prepared by the following methods: 25 DMF (N, N-dimethylformamide) powder of mL and PVDF (polyvinylidene fluoride) powder of 3.5 g were added in a beaker and a magnet was added thereto, and the mixture was sufficiently stirred at 50℃on a heated magnetic stirrer for 4 h, and further 1 g PVP (polyvinylpyrrolidone) was added thereto for further sufficient stirring for 8 h, and after the stirring was completed, a uniform casting solution was obtained, and the casting solution was subjected to vacuum pretreatment to eliminate bubbles in the casting solution and cast on a glass substrate to a thickness of 250 μm by a doctor blade, and then a glass plate was immersed in deionized water to form a film.
Performance testing
The samples prepared in examples 1-7 and comparative examples 1-2 were tested for electrical, thermal and electromagnetic shielding as follows:
conductivity coefficient: conductivity was measured according to ASTM D257. Thus, the resistivity was measured to be higher than 100M Ω using gemini 6517A, and for lower values, gemini 2100 (the Ji. In cleveland, ohio) was used.
Thermal conductivity coefficient: thermal conductivity was measured by Laser Flash (LFA) and LFA447 (Netzsch GmbH, selb, germany). Five shots, each 30 ms in duration, were used and the signal was installed with the Proteus analysis software (Netzsch GmbH, selb, germany) by the cope-Lehman algorithm.
Electromagnetic shielding: EMI shielding test high frequency EMI shielding measurements were made according to ASTM D4935-99 using an ENA series network analyzer E5061B (100 kHz-3 GHz), japan agilent technologies, inc, and using a us HP 8720C network analyzer (50 MHz-20 GHz).
The test results were as follows:
as can be seen from the table, the conductivity of the non-copper plated graphene nonwoven fabric (comparative example 1) was 2.7X10 4 S m -1 A thermal conductivity of 3X 10 2 W m -1 K -1 The electromagnetic interference shielding effectiveness is 26dB; copper plating (comparative example 2) on the nonconductive and nonconductive film to form a material having an electrical conductivity of 1.2X10 5 S m -1 A thermal conductivity of 1.7X10 2 W m -1 K -1 The electromagnetic interference shielding effectiveness is 18dB; and the conductivity of the composite graphene nonwoven fabric (example 1-example 7) obtained by copper plating on the graphene nonwoven fabric was 7.4X10 5 S m -1 The heat conductivity is 5.9X10 2 W m -1 K -1 The electromagnetic interference shielding effectiveness is above 36dB, and the performance of the composite graphene non-woven fabric prepared by the method is greatly improved.
The preferred embodiments of the present invention have been described in detail above with reference to the examples, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (9)
1. The preparation method of the composite graphene non-woven fabric is characterized by comprising the following steps of:
s1, uniformly dispersing graphene oxide fibers in an aqueous solvent, and then filtering and depositing through a filter screen to obtain graphene oxide fiber non-woven fabrics on the filter screen;
s2, thermally annealing the graphene oxide fiber non-woven fabric obtained in the step S1 to obtain graphene fiber non-woven fabric;
and S3, immersing the graphene fiber non-woven fabric obtained in the step S2 in an electrolytic copper plating solution to perform electroless copper plating, and then cleaning and drying to obtain the graphene fiber non-woven fabric.
2. The method for preparing a composite graphene nonwoven fabric according to claim 1, wherein in step S1, the method for preparing graphene oxide fibers comprises:
s1.1, dispersing graphene oxide in N, N-dimethylformamide to prepare spinning solution, wherein the mass volume ratio of the graphene oxide to the N, N-dimethylformamide is 1: (3-5);
s1.2, adjusting the injection and rotation speed ratio 1: and (140-420), enabling the spinning solution to enter ethyl acetate coagulating liquid to be coagulated into filaments, and obtaining the graphene oxide fibers.
3. The method for preparing a composite graphene non-woven fabric according to claim 1, wherein in step S1, the aqueous solvent comprises the following components in volume ratio (1-3): 1 water and ethanol.
4. The method for preparing the composite graphene non-woven fabric according to claim 1, wherein in the step S2, the thermal annealing temperature is 1000-3500 ℃ for 2 hours.
5. The method for preparing the composite graphene non-woven fabric according to claim 1, wherein in the step S3, the copper solution comprises the following components in percentage by mass (23-25): 4: copper sulfate pentahydrate (90-93), formaldehyde solution and disodium ethylenediamine tetraacetate dihydrate, and the pH is 12.0-12.5.
6. The method for preparing a composite graphene non-woven fabric according to claim 5, wherein in the step S3, copper plating treatment is performed at 40-50 ℃ for 1-10 minutes.
7. The method for producing a composite graphene nonwoven fabric according to any one of claims 1 to 6, wherein the following pretreatment is further performed before copper plating the graphene fiber nonwoven fabric obtained in step S2: immersing the non-woven fabric in a molar concentration ratio of 1:1, in the mixed solution of tin chloride and hydrochloric acid for 0.5-1 h, cleaning and drying, and immersing in a molar concentration ratio of 7:1250 and hydrochloric acid for 0.5 to 1 hour, and then cleaning and drying.
8. The composite graphene nonwoven fabric produced by the production method of any one of claims 1 to 7.
9. The use of the composite graphene nonwoven fabric of claim 8 for the preparation of lightning strike protection, heat sinks in electronic devices, or heat transfer conductive elements.
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