CN110923679A - Graphene-loaded nano copper particle composite material and preparation method thereof - Google Patents
Graphene-loaded nano copper particle composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1889—Multistep pretreatment with use of metal first
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Abstract
A graphene loaded nano-copper particle composite material and a preparation method thereof are disclosed, the composite material is composed of a graphene sheet layer and a chemical coating on the surface of the graphene sheet layer, and the chemical coating is nano-copper with a face-centered cubic structure; the preparation method comprises the following steps: (1) immersing graphene into water for ultrasonic dispersion, then putting the graphene into a sensitizing solution, and carrying out sensitization treatment at 90-100 ℃; (2) taking the sensitized graphene out, washing with water, and then putting the sensitized graphene into an activating solution to be stirred and activated to obtain activated graphene; (3) taking out the activated graphene, washing with water, and then placing in a plating solution containing main salt and reducing agent components; (4) heating the plating solution, adjusting the pH value and preserving heat; (5) and washing and drying the copper-plated graphene. The method can realize the stable combination between the graphene and the nano copper particles; the surface defects of the graphene are repaired, and the comprehensive performance of the graphene is improved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a graphene loaded nano copper particle composite material and a preparation method thereof.
Technical Field
In recent years, the requirements for material performance in the fields of machinery, electronic information, energy storage, aerospace and the like are higher and higher, and the research of high-performance and multipurpose composite materials becomes a hotspot in the field of material research; the copper-based composite material has excellent heat conduction and electric conduction performance, is widely applied to the industrial fields of electronics, electricity, mechanical manufacturing, construction, national defense and the like, and becomes one of important varieties and research hotspots in the field of metal-based composite materials.
The graphene is SP2The thickness of the two-dimensional monolayer atomic crystal material with the hexagonal honeycomb structure formed by closely packing carbon atoms is only 0.3345nm, the material is the thinnest two-dimensional material at present, and the material is also used for constructing SP (SP) such as fullerene, carbon nano tube, graphite and the like2A base component of a hybrid carbon allotrope material; due to the unique structure of the graphene, the graphene has extremely excellent conductivity, mechanical property, heat conductivity and ultrahigh specific surface area, is an ideal reinforcement of a composite material, and has wide application prospects in the aspects of energy storage materials, high-toughness materials, nano materials, friction materials and the like. Therefore, the preparation of the graphene/copper composite material can obviously improve the comprehensive performance of the copper-based composite material and expand the application field of the copper-based composite material.
The graphene/metal composite materials are mainly divided into two main categories, namely graphene-loaded nano metal particle composite materials and graphene-reinforced metal matrix composite materials. Nano metal particles are receiving more and more attention due to their unique optical, electrical and catalytic properties. However, the nano metal particles are very easy to agglomerate due to the extremely high surface energy, and cannot be uniformly dispersed in the matrix in the preparation process of the composite material. Due to the unique two-dimensional planar lamellar structure, the extremely high specific surface area and the surface wrinkles of the graphene, the graphene becomes an ideal carrier for loading inorganic nanoparticles, and can effectively prevent the agglomeration of nano metal particles.
Due to the particularity of the preparation method, the redox graphene has more structural defects and oxygen-containing functional groups on the surface of the graphene, and the performance of the graphene can be reduced due to the defects and the oxygen-containing functional groups; due to the extremely poor wettability between the metal copper and the graphene, no diffusion or reaction exists between adjacent interfaces of the graphene and the metal copper, the interface between the graphene and the copper is difficult to bond, the bonding force of the interface is weak, and the performance of the composite material is seriously influenced.
Disclosure of Invention
Aiming at the problems in the existing graphene metal composite material preparation technology, the invention provides a graphene loaded nano copper particle composite material and a preparation method thereof, and the stable combination of copper and graphene is realized through sensitization and activation treatment.
The graphene-loaded nano-copper particle composite material is of a sheet structure and is composed of a graphene sheet layer and a chemical coating on the surface of the graphene sheet layer, wherein the chemical coating is a copper coating, the copper coating is nano-copper particles with a face-centered cubic structure, and the particle size of the nano-copper particles is 30-200 nm.
The graphene-loaded nano copper particle composite material comprises 14-40% by mass of graphene and the balance of a copper coating.
The preparation method of the graphene loaded nano-copper particle composite material comprises the following steps:
(1) immersing graphene in water, performing ultrasonic dispersion treatment on the graphene, taking out the graphene, putting the graphene into a sensitizing solution, and performing sensitization treatment for 5-10 min at 90-100 ℃ to obtain sensitized graphene; the sensitizing solution is composed of SnCl2The solution is mixed with hydrochloric acid to form SnCl2The concentration of the solution is 10-30 g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.01-0.03;
(2) taking out the sensitized graphene, washing with water until the washing liquid is neutral, then placing the sensitized graphene into an activating solution, and activating for 4-10 min under the stirring condition to obtain activated graphene; the activating solution is prepared from AgNO3Preparation of solution and aqueous ammonia, AgNO3The concentration of the solution is 1-2 g/L, and the dosage of ammonia water is determined according to NH in the activation solution3·H2O and AgNO3Is 2;
(3) taking out the activated graphene, washing with water until the washing liquid is neutral, and then placing in a plating solution; the plating solution is prepared by adding main salt CuSO4·5H2O, reducing agent formaldehyde solution, complexing agent EDTA.2Na and complexing agent C4H4KNaO6And stabilizer 2, 2-bipyridine in water, CuSO4·5H2The dosage of O is 12.5-37.5 g/L of water, the dosage of the formaldehyde solution is 16-48 mL/L of water, the dosage of EDTA-2 Na is 20-60 g/L of water, and C4H4KNaO6The dosage of the 2, 2-bipyridine is 10-30 g/L of water, and the dosage of the 2, 2-bipyridine is 1-3 g/L of water;
(4) heating the plating solution to 35-45 ℃ under the stirring condition, then dropwise adding NaOH solution to adjust the pH value to 12-13, and then preserving heat for 30-40 min to form copper-plated graphene in the plating solution;
(5) and washing the copper-plated graphene until the washing liquor is neutral, and then drying to remove water to prepare the graphene-loaded nano copper particle composite material.
In the step (1), the ultrasonic frequency during ultrasonic dispersion treatment is 35-53 kHz; the ultrasonic treatment time is 10-30 min.
In the step (1), when the graphene is immersed in water, the solid-to-liquid ratio of the graphene to the water is 1.5-2.5 g/L.
In the step (5), the temperature of vacuum drying is 100 +/-2 ℃, and the time is 1-3 h.
The mass concentration of the hydrochloric acid is above 36%.
The mass concentration of the formaldehyde solution is 37-40%.
The above NaOH solution had a concentration of 1M.
Compared with the prior art, the invention has the following characteristics and positive effects:
(1) the surface of the graphene can be uniformly covered with a copper coating without exposed graphene, the nano copper particles are uniformly distributed on the copper coating, and the graphene and the nano copper particles are compounded through the copper coating, so that the graphene and the nano copper particles can be stably combined;
(2) the oxygen-containing functional groups on the surface of the redox graphene are reduced in the chemical plating process, the surface structure defects can be repaired to a certain extent, the graphene structure is more complete, and the comprehensive performance of the graphene is improved;
(3) the preparation method is simple in process, rapid and efficient, and the prepared graphene loaded nano-copper particle composite material is expected to be independently applied to the field of solid lubrication and can also be used as a reinforcement material to prepare a novel composite material; the specific gravity of the material can be increased due to the attachment of copper on the surface of the graphene, the problem of poor wettability between the graphene and the metal matrix can be effectively solved, and the dispersibility of the graphene in the matrix is improved.
Drawings
Fig. 1 is an SEM photograph of a graphene-supported nano-copper particle composite material prepared in example 1 of the present invention;
fig. 2 is an SEM photograph of the graphene-supported nano-copper particle composite material prepared in example 2 of the present invention;
fig. 3 is an XRD pattern of the graphene-supported nano-copper particle composite material and graphene prepared in example 2 of the present invention; in the figure, the upper part is the graphene loaded nano copper particle composite material, and the lower part is the graphene;
fig. 4 is a Raman chart of the graphene-supported nano copper particle composite material and graphene prepared in example 2 of the present invention, wherein ▲ is the graphene-supported nano copper particle composite material, and ● is graphene;
fig. 5 is an FTIR plot of graphene-supported nanocopper particle composites and graphene prepared in example 2 of the present invention; in the figure, graphene is arranged on the upper part, and the graphene loaded nano copper particle composite material is arranged on the lower part;
fig. 6 is an SEM photograph of the graphene-supported nano copper particle composite material prepared in example 3 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
The device used for observing the microscopic morphology in the embodiment of the invention is an Ultra Plus type field emission scanning electron microscope.
The apparatus used for the phase analysis in the examples of the present invention was a powder X-ray diffractometer model PANalytical X' Pert Pro.
The equipment adopted for infrared spectroscopic analysis in the embodiment of the invention is an Agilent-660FTIR type FTIR analyzer.
The equipment adopted for Raman spectrum analysis in the embodiment of the invention is an HR800 Raman spectrometer.
The graphene adopted in the embodiment of the invention is commercially available redox graphene.
All chemical reagents used in the examples of the present invention were commercially available analytical reagents.
The water used in the embodiment of the invention is deionized water.
In the embodiment of the invention, a vacuum drying oven is adopted for drying.
The ultrasonic frequency during ultrasonic dispersion treatment in the embodiment of the invention is 35-53 kHz.
The mass concentration of the ammonia water in the embodiment of the invention is more than 25%.
In the embodiment of the invention, the mass concentration of the formaldehyde solution is 37-40%.
Example 1
Immersing graphene in water, and carrying out ultrasonic dispersion treatment on the graphene for 10min, wherein the solid-liquid ratio of the graphene to the water is 2 g/L; then taking out the graphene, putting the graphene into a sensitizing solution, and carrying out sensitization treatment for 10min at 90 ℃ to obtain sensitized graphene;
the sensitizing solution is composed of SnCl2The solution is mixed with hydrochloric acid to form SnCl2The concentration of the solution is 10g/L, the mass concentration of hydrochloric acid is more than 36%, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.01;
taking out the sensitized graphene, washing with water until the washing liquid is neutral, then placing the sensitized graphene into an activating solution, and activating for 4min under the condition of stirring to obtain activated graphene;
the activating solution is AgNO3Silver ammonia solution, AgNO, from solution and ammonia water3The concentration of the solution is 1g/L, and the dosage of ammonia water is NH3·H2O and AgNO3Is 2;
adding main salt CuSO4·5H2O, reducing agent formaldehyde solution, complexing agent EDTA.2Na and complexing agent C4H4KNaO6And stabilizer 2, 2-dipyridine are dissolved in water to prepare plating solution; CuSO4·5H2The dosage of O is 12.5g/L of water, the dosage of the formaldehyde solution is 16mL/L of water, the dosage of EDTA-2 Na is 20g/L of water, C4H4KNaO6The dosage of the water is 10g/L, 2The amount of bipyridine used is 1g/L of water;
taking out the activated graphene, washing with water until the washing liquid is neutral, and then placing in a plating solution;
heating the plating solution to 35 ℃ under the condition of stirring, then dropwise adding NaOH solution to adjust the pH value to 13, and then preserving the temperature for 30min to form copper-plated graphene in the plating solution;
washing copper-plated graphene until washing liquor is neutral, and then drying at 100 +/-2 ℃ for 1h to remove water to prepare the graphene-loaded nano copper particle composite material; the graphene-loaded nano-copper particle composite material is of a sheet structure and is composed of a graphene sheet layer and a chemical coating on the surface of the graphene sheet layer, wherein the chemical coating is a copper coating, the copper coating is nano-copper particles with a face-centered cubic structure, and the particle size of the nano-copper particles is 30-80 nm; wherein the mass percent of the graphene is 40%, and the balance is a copper plating layer; the SEM photograph is shown in FIG. 1.
Example 2
The method is the same as example 1, except that:
(1) performing ultrasonic dispersion treatment for 30min, wherein the solid-to-liquid ratio of graphene to water is 2.5 g/L; sensitizing at 95 deg.C for 8 min;
(2)SnCl2the concentration of the solution is 20g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.02;
(3) activating for 7 min; AgNO used for activating liquid3The concentration of the solution is 1.5 g/L;
(4) CuSO for preparing plating solution4·5H2The dosage of O is 25g/L of water, the dosage of the formaldehyde solution is 32mL/L of water, the dosage of EDTA-2 Na is 40g/L of water, C4H4KNaO6The dosage of the 2, 2-bipyridyl is 20g/L of water, and the dosage of the 2, 2-bipyridyl is 2g/L of water;
(5) heating the plating solution to 40 ℃, dropwise adding NaOH solution to adjust the pH value to 12.5, and then keeping the temperature for 35 min;
(6) drying for 2h at 100 +/-2 ℃; 29% of graphene in the graphene-loaded nano-copper particle composite material by mass; the particle size of the nano copper particles is 30-200 nm, and an SEM photograph is shown in figure 2;
the XRD contrast of the graphene and graphene supported nano-copper particle composite material is shown in fig. 3; as can be seen from the figure, the drawing,an impurity C peak with a non-graphene structure exists on the surface of the graphene; the impurity C peak on the surface of the composite material is obviously weakened, the characteristic peak intensity of the copper crystal is large, the existence of copper is proved, and the diffraction peak width is widened due to the nanoscale copper particles; at the same time, Cu appears on the surface due to oxidation of copper and the like2A characteristic peak of O;
the Raman spectrum of the graphene and graphene loaded nano copper particle composite material is shown in fig. 4; in Raman spectroscopy of graphene, the intensity ratio (I) of the D peak and the G peak is generally usedD/IG) Characterizing structural defects of graphene, ID/IGThe smaller the value, the lower the defect density; by the pair ID/IGCalculating to obtain the result that the graphene is chemically plated ID/IGThe defect density of the graphene surface can be reduced from 1.367 to 1.187, which shows that the defect density of the graphene surface can be reduced through electroless plating; by analyzing the structures of the graphene before and after chemical plating through Raman spectroscopy, the chemical plating on the surface of the graphene not only has no influence on the inherent structure of the graphene and has no new defect introduced, but also has certain repair on the defect on the surface of the graphene, and can effectively reduce the defect concentration on the surface of the graphene;
the FTIR spectrum of the graphene and graphene supported nano-copper particle composite material is shown in fig. 5; oxygen-containing functional groups such as C-O, C-O, O-H exist on the surface of the graphene, after chemical plating, the strength of the oxygen-containing functional groups is obviously reduced, and characteristic peaks of partial oxygen-containing functional groups disappear, so that the repairing effect of the chemical plating process on the surface defects of the graphene is further explained.
Example 3
The method is the same as example 1, except that:
(1) performing ultrasonic dispersion treatment for 20min, wherein the solid-to-liquid ratio of graphene to water is 1.5 g/L; sensitizing at 100 deg.C for 5 min;
(2)SnCl2the concentration of the solution is 30g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.03;
(3) activating for 10 min; AgNO used for activating liquid3The concentration of the solution is 2 g/L;
(4) CuSO for preparing plating solution4·5H2Use of O37.5g/L of water, 48mL/L of water as formaldehyde solution, 60g/L of water as EDTA-2 Na and C4H4KNaO6The dosage of the 2, 2-bipyridyl is 30g/L of water, and the dosage of the 2, 2-bipyridyl is 3g/L of water;
(5) heating the plating solution to 45 ℃, dropwise adding NaOH solution to adjust the pH value to 12, and then preserving the temperature for 40 min;
(6) drying for 3h at 100 +/-2 ℃; the mass percent of graphene in the graphene-loaded nano-copper particle composite material is 14%; the particle size of the nano-copper particles is 30-40 nm, and the SEM photograph is shown in figure 6.
Claims (8)
1. The graphene-loaded nano-copper particle composite material is characterized by comprising a graphene sheet layer and a chemical coating on the surface of the graphene sheet layer, wherein the chemical coating is a copper coating, the copper coating is nano-copper particles with a face-centered cubic structure, and the particle size of the nano-copper particles is 30-200 nm.
2. The graphene-supported nano-copper particle composite material as claimed in claim 1, wherein the graphene-supported nano-copper particle composite material comprises 14-40% by mass of graphene, and the balance of copper plating.
3. The preparation method of the graphene-supported nano copper particle composite material of claim 1 is characterized by comprising the following steps:
(1) immersing graphene in water, performing ultrasonic dispersion treatment on the graphene, taking out the graphene, putting the graphene into a sensitizing solution, and performing sensitization treatment for 5-10 min at 90-100 ℃ to obtain sensitized graphene; the sensitizing solution is composed of SnCl2The solution is mixed with hydrochloric acid to form SnCl2The concentration of the solution is 10-30 g/L, and the hydrochloric acid and SnCl2The volume ratio of the solution is 0.01-0.03;
(2) taking out the sensitized graphene, washing with water until the washing liquid is neutral, then placing the sensitized graphene into an activating solution, and activating for 4-10 min under the stirring condition to obtain activated graphene; the activating solution is prepared from AgNO3Preparation of solution and aqueous ammonia, AgNO3The concentration of the solution is 1-2 g/L, and the dosage of ammonia water is NH3·H2O and AgNO3Is 2;
(3) taking out the activated graphene, washing with water until the washing liquid is neutral, and then placing in a plating solution; the plating solution is prepared by adding main salt CuSO4·5H2O, reducing agent formaldehyde solution, complexing agent EDTA.2Na and complexing agent C4H4KNaO6And stabilizer 2, 2-bipyridine in water, CuSO4·5H2The dosage of O is 12.5-37.5 g/L of water, the dosage of the formaldehyde solution is 16-48 mL/L of water, the dosage of EDTA-2 Na is 20-60 g/L of water, and C4H4KNaO6The dosage of the 2, 2-bipyridine is 10-30 g/L of water, and the dosage of the 2, 2-bipyridine is 1-3 g/L of water;
(4) heating the plating solution to 35-45 ℃ under the stirring condition, then dropwise adding NaOH solution to adjust the pH value to 12-13, and then preserving heat for 30-40 min to form copper-plated graphene in the plating solution;
(5) and washing the copper-plated graphene until the washing liquor is neutral, and then drying to remove water to prepare the graphene-loaded nano copper particle composite material.
4. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein in the step (1), the ultrasonic frequency during ultrasonic dispersion treatment is 35-53 kHz; the ultrasonic treatment time is 10-30 min.
5. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein in the step (1), when the graphene is immersed in water, the solid-to-liquid ratio of the graphene to the water is 1.5-2.5 g/L.
6. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein in the step (5), the temperature of vacuum drying is 100 +/-2 ℃ and the time is 1-3 h.
7. The method for preparing a graphene-supported nano copper particle composite material according to claim 3, wherein the mass concentration of the hydrochloric acid is 36% or more.
8. The preparation method of the graphene-supported nano copper particle composite material according to claim 3, wherein the mass concentration of the formaldehyde solution is 37-40%.
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| CN111690324A (en) * | 2020-07-21 | 2020-09-22 | 宁波计氏金属新材料有限公司 | Corrosion-resistant chromium-free coating and surface treatment process thereof |
| CN112624096A (en) * | 2020-12-23 | 2021-04-09 | 西安交通大学 | Graphene surface dispersibility modification method |
| CN115896880A (en) * | 2022-11-23 | 2023-04-04 | 山东大学 | Method for preparing nano-copper/graphene composite coating by using pulse brush plating technology |
| CN116851748A (en) * | 2023-07-19 | 2023-10-10 | 西南交通大学 | Nano metal particle modified graphene conductivity enhancement copper-based composite material and high-temperature high-pressure preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111593226A (en) * | 2020-06-16 | 2020-08-28 | 江西省科学院应用物理研究所 | Graphene/copper composite material and preparation method thereof |
| CN111690324A (en) * | 2020-07-21 | 2020-09-22 | 宁波计氏金属新材料有限公司 | Corrosion-resistant chromium-free coating and surface treatment process thereof |
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| CN115896880B (en) * | 2022-11-23 | 2024-06-04 | 山东大学 | Method for preparing nano copper/graphene composite coating by using pulse brush plating technology |
| CN116851748A (en) * | 2023-07-19 | 2023-10-10 | 西南交通大学 | Nano metal particle modified graphene conductivity enhancement copper-based composite material and high-temperature high-pressure preparation method thereof |
| CN116851748B (en) * | 2023-07-19 | 2024-02-09 | 西南交通大学 | Modified graphene conductivity-enhanced copper-based composite material and preparation method thereof |
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