CN114101666A - Graphene-based silver-saving electrical contact material and manufacturing method thereof - Google Patents
Graphene-based silver-saving electrical contact material and manufacturing method thereof Download PDFInfo
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Abstract
The graphene-based silver-saving electrical contact material is characterized by comprising 10.1-98 wt% of graphene and an additive, wherein the additive comprises one or more of Au, Ag, Cu, Ti, CdO, SnO2, ZnO, NI, Zr, W, Mo, V, Nb, Ta, rare earth metals and graphite or an alloy and a compound thereof. Compared with the traditional silver-based electrical contact material, the graphene-based silver-saving electrical contact material provided by the invention has the advantages that the comprehensive performance is improved, particularly, the silver can be saved by 10-100%, the purpose of silver-free/less silver replacement is realized, and the cost is greatly reduced.
Description
Technical Field
The invention belongs to the field of electrical materials, particularly the field of electrical contact materials, and relates to a graphene-based silver-saving electrical contact material and a manufacturing method thereof.
Background
The electrical contact material can be roughly divided into the following low-voltage electrical contact material, medium-voltage and high-voltage electrical contact material, vacuum contact material and weak electrical contact material according to application. The low-voltage contact material is a silver-based electrical contact material which basically uses noble metal silver as a matrix. It requires electrical contact materials with high electrical conductivity, low contact resistance, high thermal conductivity, abrasion resistance, impact resistance, and reliable chemistry. The electric contact material has been used for more than 100 years, and pure silver, pure gold and pure platinum are used as the raw materials of the electric contact. The alloys of Ag-Cu, PtI-Ag and Pd-Ag were used in the beginning of the 40 s, and multi-element noble metals and various noble metal composites were developed since the 60 s. The maximum application range of the silver-based electrical contact material is far higher than that of other electrical contact materials. The metal silver has high electrical conductivity, good thermal conductivity, reliable chemical stability under atmospheric conditions and good oxidation resistance. Although the comprehensive physical properties of silver are most suitable for preparing the electrical contact material, silver is a noble metal and is expensive and has poor mineral resources, and the silver-based electrical contact material needs a large amount of silver as a raw material and is too expensive.
The electrical contact is one of the core components of electrical switches and instruments and meters, and is mainly responsible for the important tasks of breaking and connecting circuits and load currents. The requirements of electrical contact materials are manifold, i.e. they have good electrical and thermal conductivity, low and stable contact resistance, high resistance to erosion, welding and good mechanical strength. The silver metal has good electric conduction and heat conduction performance and good oxidation resistance, and is the most main electric contact material at the present stage. However, due to the scarcity of silver resources, high price and extremely high cost, the development of silver-free/less silver-saving electrical contact materials is of great significance. Copper has good heat conduction and electric conduction performance and low price, and is a candidate material for replacing silver-based electrical contacts. There have been attempts to replace silver with inexpensive copper metal, but copper is easily oxidized to form copper oxide and cuprous oxide with low conductivity due to poor chemical stability, and the electrical contact resistance is increased, the conductivity is deteriorated, the temperature rise is very high, and fusion welding occurs. It is easy to cause major accidents. In addition, the traditional copper and the alloy thereof have poor mechanical properties, poor fusion welding resistance and breaking resistance, and greatly reduce the service life and reliability of equipment, so that the attempt is not widely popularized and applied. Therefore, the research and development of silver-free/silver-less silver-saving electrical contact materials becomes a modern task.
Graphene is the only existing environment-friendly novel carbon material with a two-dimensional honeycomb lattice structure formed by densely stacking carbon atoms, the thickness of the novel carbon material is usually within 10nm, the novel carbon material has an ultra-large specific surface area, the novel carbon material is the material with the highest strength known at present and reaches 130GPa, the current-carrying mobility reaches 150000cm2/VS, and the thermal conductivity reaches 5150w (m.K). Therefore, the unique nanostructure and electrical properties of the silver alloy have higher electrical conductivity, thermal conductivity and mechanical properties than silver due to chemical properties, thermal properties, mechanical properties and the like. Particularly, in China, the graphene is already industrialized and the application is gradually expanded, so that the cost of the graphene is gradually reduced and reaches about one third of the silver value at present, and the trend is that the silver value is higher and the graphene value is lower and lower. The characteristics of the graphene which are unique and superior to the silver become ideal materials for replacing the silver.
In recent years, graphene has been disclosed as a small amount (less than 10.1% Wt) of additive (reinforcing agent and modifier) for silver-based and copper-based electrical contact materials, and for example, chinese patents CN102385938A, CN105719854A, CN105525132A, CN105385883A, CN105551839A, CN105483422A, CN105603247A and CN105483641A have all involved the problems.
The invention aims to provide a silver-free/silver-less silver-saving graphene-based electrical contact material which is free of silver and has the advantages of good electrical conductivity, low contact resistance, good chemical stability, good fusion welding resistance, high hardness and easiness in preparation, and is prepared by metal-coated graphene and an additive.
Disclosure of Invention
In order to achieve the purpose of saving silver, the invention discloses a graphene-based silver-saving electrical contact material which uses graphene to replace silver (no silver or less silver).
The technical scheme of the invention is as follows:
the graphene-based silver-saving electrical contact material is characterized by comprising 10.1-98 wt% of graphene and an additive, wherein the additive comprises one or more of Au, Ag, Cu, Ti, CdO, SnO2, ZnO, NI, Zr, W, Mo, V, Nb, Ta, rare earth metals and graphite or an alloy and a compound thereof. Through a large number of experiments, the electric contact made by selecting the graphene with the component proportion of 10.1-98 wt% has the best effect and lower cost, if the graphene is too small, the purpose of saving precious metal silver and reducing the cost is not achieved, meanwhile, the electric conductivity and the heat conductivity of the electric contact are obviously reduced, the wear resistance is also reduced, and therefore, the quality of the electric contact is reduced, and the electric contact is not suitable for batch production.
Furthermore, the graphene and the additive are in a powder particle form, the purity of the additive powder is 99.99%, the particle size is required to be 3nm-3 μm, and the graphene and the additive powder particles are coated by metal.
Further, graphene is an N layer, and N is 1 to 10.
A method of making a graphene-based, silver-saving electrical contact material, comprising:
s1, cleaning the metal target material, immersing the target material in dilute sulfuric acid, taking out after immersing for a period of time, washing with deionized water, washing with acetone and drying;
s2, fixing the clean target material on a target frame of a high-power pulse magnetron plasma sputtering instrument;
s3, vacuumizing the plasma sputtering instrument, and starting a heater to reach the temperature of 300-500 ℃ when the vacuum degree of a cavity of the plasma sputtering instrument reaches a preset value, wherein the rotating speed of the workpiece frame is 5-8 rpm;
s4, sputtering target materials by using a plasma sputtering instrument, and respectively generating metal-coated powder particles on the graphene and the additive powder;
s5, putting the graphene prepared in the S4 and the metal-coated powder particles of the additive into a ball milling tank of a ball milling powder mixer, and mixing the powder for 8-12 hours under the protection of high-purity argon atmosphere;
s6, carrying out isostatic pressing pre-forming on the mixed metal-coated powder particles at the forming pressure of 150-300 mPa, and prefabricating an extrusion blank;
s7, sintering the extrusion blank under the protection of high-purity argon or hydrogen gas, and then preserving heat;
s8, carrying out hot extrusion deformation on the sintered blank;
s9, preserving the heat of the extruded and deformed blank for 1.5h, and cooling to 350 ℃;
s10: and rolling and drawing to obtain the graphene-based silver-saving electrical contact material.
Further, in step S1, the dilute sulfuric acid concentration is 10-30%, and the soaking time is 5-10 minutes.
Further, in step S3, the vacuum degree of the cavity of the plasma sputtering apparatus needs to reach (1-4) × 10-3Pa。
Further, in step S4, high-purity argon gas is introduced into the cavity of the plasma sputtering apparatus, and when the vacuum degree is 0.3 to 0.9Pa, the plasma sputtering power supply is started, the bias voltage is adjusted to 600 to 1000V, and sputtering is performed for 5 to 60 minutes.
Further, in step S7, the sintering temperature is 750-.
Further, in step S8, the extrusion temperature is 650-: 1.
further, the method for preparing the metal-coated graphene and the additive powder may further adopt a mechanical ball milling method, a chemical reduction method, a thermal treatment reduction method, a spraying method, a chemical vapor deposition method, and a physical vapor deposition method.
Further, the purity of the high-purity argon is 99.99%.
Further, the metal target material comprises Au, Ag, Ti, Cd, Sn, Zn, NI, Zr, W, Mo, V, Nb, Ta and rare earth metal, wherein the purity of the target material is 99.99%.
Further, the rolling procedure in S10 adopts a hot rolling temperature of 700-.
Compared with the silver-based electrical contact material, the graphene-based silver-saving electrical contact material does not contain or contain a small amount of silver, reduces the contact resistance, reduces the cutting action of the additive on the substrate, and improves the easy agglomeration, uneven distribution, interface bonding force with the additive powder and wettability of the graphene by the metal-coated graphene powder and the coating additive powder generated by plasma sputtering deposition. The metal-coated powder particles generated by plasma sputtering deposition improve the easy agglomeration and uneven distribution of graphene, the interface bonding force and wettability between the graphene and the additive, reduce the splitting effect of the additive on a matrix, and are beneficial to obtaining good interface bonding, so that the conductivity, the heat conduction performance and the arc erosion resistance of the graphene-based silver-saving electrical contact material are improved, and the processing performance of the graphene-based silver-saving electrical contact material is effectively improved. Improve the welding resistance, the electric arc burning resistance and the mechanical performance.
Drawings
Fig. 1 is a preparation flow chart of the graphene-based silver-saving electrical contact material.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
Preparing graphene CdO, wherein the graphene CdO contains 70wt percent of graphene
S1, cleaning the target material, wherein the target material is silver (Ag), and the purity of the target material is 99.99%; s2, fixing the clean target material silver on a target frame of the high-power pulse magnetron plasma sputtering instrument; s3, vacuumizing the plasma sputtering instrument, wherein the vacuum degree in the cavity of the plasma sputtering instrument reaches 4 multiplied by 10-3Is turned on at PaThe heater is heated to 350 ℃, and the rotating speed of the workpiece frame is 5 rpm; s4, introducing high-purity argon gas (purity is 99.99%, the same below) into a cavity of a plasma sputtering instrument, starting a plasma sputtering power supply when the vacuum degree is 0.3Pa, adjusting the bias voltage to 700V, starting sputtering, sputtering a metal silver target material, and depositing on graphene powder and CdO powder respectively to generate silver-coated graphene and CdO powder, wherein the content of the silver-coated graphene and the CdO powder reaches a set value; s5, putting the silver metal coated graphene powder particles and the coating additive CdO powder particles prepared in the step S4 into a ball milling powder mixer together, wherein high-purity argon gas is required to be introduced for protection, the powder mixing rotation speed is 100-250r/min, the ball milling is carried out for 15-20 minutes, the ball milling is stopped for 5 minutes, the clockwise and anticlockwise alternate rotation is carried out, and the powder mixing time is 10 hours in total to obtain the mixed particles of the coated silver graphene and the additive CdO powder; s6, carrying out isostatic pressing on the mixed powder particles under the pressure of 250MPa to prepare an extrusion blank; s7, sintering the blank again, and keeping the temperature at 750 ℃ for 5 hours under the protection of high-purity argon; s8, carrying out hot extrusion deformation on the sintered blank after heat preservation for 2h at 800 ℃ under the protective atmosphere, wherein the extrusion ratio is 100 to 1; s9, preserving the heat of the extruded and deformed blank for 1.5h, and cooling to 350 ℃; and S10, performing deformation such as cold rolling and drawing to obtain the graphene-based cadmium oxide electrical contact material, wherein the rolling process adopts hot rolling, and the transverse rolling is performed for 5 times, the longitudinal rolling is performed for 5 times, and the transverse rolling and the longitudinal rolling are performed alternately to realize silver saving by 70%.
Example 2
Preparation of graphene Sn2Contact material containing 55 wt% of graphene
This example is the same as example 1, except that CdO is changed to SnO2The target material is changed into nickel. Changing bias voltage in S4 to 750V, and sputtering and depositing nickel-coated graphene powder particles prepared by S4 plasma and SnO serving as additive2Directly carrying out isostatic pressing on the powder mixed particles, and sintering for 3h at the sintering temperature of 850 ℃ under the pressure of 300Mpa and the protection of argon; hot extrusion temperature 800 ℃, extrusion ratio 100: 1, rolling, drawing and other working procedures are carried out to finally obtain silver-free graphene SnO2An electrical contact material. The silver can be saved by 55 percent.
Example 3
Preparing a graphene tungsten electrical contact material containing 60 wt% of graphene
The operation procedure of S1 is the same as that of example 1, but the target material is changed to tungsten material. Changing the bias voltage of S4 in example 1 to 950v, and performing plasma sputtering deposition for 55min to prepare tungsten-coated graphene powder particles; s3, ball milling, namely putting tungsten-coated graphene powder particles into a ball milling tank, and ball milling for 4 hours under the protection of high-purity argon; s4, putting the ball-milled powder particles into a die for isostatic pressing, wherein the pressure is 200 Mpa; s5, sintering the blank obtained after isostatic cool pressing in a high-purity argon protective atmosphere at 1050 ℃ for 6 h; s6 changing the secondary repressing pressure to 250 Mpa; s7, carrying out secondary sintering on the pressed blank under the protective atmosphere of high-purity argon at 1050 ℃ for 6 h; s8, carrying out hot extrusion on the obtained blank under the protection of high-purity argon, wherein the hot extrusion temperature is 850 ℃, and the extrusion ratio is 100: 1, extrusion speed of 5cm/min and extrusion die preheating temperature of 500 ℃. Finally, the graphene-based silver-saving electrical contact material with the graphene tungsten completely free of silver is prepared, and the silver can be saved by 60%.
Example 4
Preparing a graphene rare earth cerium oxide electrical contact material, wherein the graphene rare earth cerium oxide electrical contact material contains 90wt percent of graphene
S1, preparing zirconium-coated graphene powder particles and additive CeO2Powder particles prepared in the same manner as in example 1 except that the target material was changed to zirconium; s2, changing bias voltage to 800v, sputtering for 5 minutes to prepare zirconium-coated graphene powder particles and zirconium-coated additive ZnO powder particles, S3, performing ball milling, putting the zirconium-coated graphene powder particles and the zirconium-coated additive ZnO powder particles into a ball milling tank of a ball mill, and performing ball milling for 8 hours under the protection of high-purity argon; s4, putting the powder particles after ball milling in the S3 mode into a die for isostatic pressing, wherein the pressure is 200 Mpa; s5, sintering the blank obtained after isostatic cool pressing in a high-purity argon protective atmosphere at the sintering temperature of 850 ℃ for 6 hours; s6, secondary repressing pressure is 250 Mpa; s7, sintering the pressed blank for the second time in the high-purity hydrogen protective atmosphere at the sintering temperature of 850 ℃ for 6 h; s8, carrying out hot extrusion on the obtained blank under the protection of high-purity argon, wherein the hot extrusion temperature is 850 ℃, the extrusion ratio is 100: 1, extrusion speed of 5cm/min and extrusion die preheating temperature of 500 ℃. Finally preparing the graphiteThe graphene-based silver-saving electrical contact material of the alkene rare earth cerium oxide can save 90 percent of silver,
example 5
Preparing graphene niobium, wherein the graphene niobium content is 70wt percent
S1 the operation steps are the same as example 1, but the target material is changed into titanium and the additive is changed into niobium; s2, changing the S4 bias voltage of example 1 to 950v, and performing plasma sputtering deposition for 30min to prepare titanium-coated graphene powder particles and additive niobium powder particles, respectively; s3, ball milling, namely putting the titanium-coated graphene powder particles and the titanium-coated niobium powder particles into a ball milling tank together, and ball milling for 4 hours under the protection of high-purity argon; s4, putting the mixed powder particles subjected to ball milling in the S3 mode into a die, and performing isostatic pressing with the pressure of 200 MP; s5, sintering the blank obtained after isostatic cool pressing in a high-purity argon protective atmosphere at the sintering temperature of 950 ℃ for 6 hours; s6, changing the secondary repressing pressure to 300 Mpa; s7, performing secondary sintering on the pressed green body in an argon protective atmosphere at the sintering temperature of 950 ℃ for 6 hours; s8, carrying out hot extrusion on the obtained blank under the protection of argon, wherein the hot extrusion temperature is 850 ℃, the extrusion ratio is 100: 1, extrusion speed of 5cm/min and extrusion die preheating temperature of 500 ℃. Finally, the graphene niobium electrical contact material is prepared, and the silver can be saved by 70%.
Example 6
Preparing graphene zirconium electrical contact material, which contains 10.1 wt% of graphene
S1 the process is the same as that of example 1, but the additive needs to be changed into zirconium (Zr); s2, changing the bias voltage to 800v, and sputtering for 25 minutes to respectively prepare silver-coated graphene powder particles and silver-coated zirconium powder particles; s3, ball milling, namely putting the silver-coated graphene powder particles and the silver-coated zirconium powder particles into a ball milling tank of a ball mill together, introducing argon, and ball milling for 7 hours under the protection of high-purity argon; s4, putting the mixed powder particles subjected to ball milling in the S3 mode into a die for isostatic pressing, wherein the pressure is 250 Mpa; s5, sintering the blank obtained after isostatic cool pressing in a high-purity argon protective atmosphere at the sintering temperature of 850 ℃ for 9 hours; s6, secondary repressing under the pressure of 300 MPa; s7, sintering the green body obtained after re-pressing for the second time under the protection of high-purity argon, wherein the sintering temperature is 850 ℃, and the sintering time is 6 hours; s8, carrying out hot extrusion on the obtained blank under the protection of high-purity argon, wherein the hot extrusion temperature is 850 ℃, and the extrusion ratio is 100: 1, extrusion speed of 6cm/min and extrusion die preheating temperature of 500 ℃. Compared with the traditional silver-based electrical contact material, the graphene-zirconium electrical contact material prepared finally can save silver by 10.1%.
Experiments prove that the 10.1% graphene can effectively reduce the production cost, ensure that the electrical contact has better electrical conductivity which can reach 48MS/m, obviously improve the wear resistance compared with the electrical contact with the content of less than 10.1%, and still have good thermal conductivity.
Example 7
Preparing graphene molybdenum containing 98 wt% of graphene
S1 the process is the same as that of example 1, but the target material is changed into nickel, and the additive material is changed into molybdenum; s2, changing bias voltage to 950v, and sputtering for 20 minutes to respectively prepare nickel-coated graphene powder particles and nickel-coated molybdenum powder particles; s3, ball milling, namely putting the nickel-coated graphene powder particles and the nickel-coated molybdenum powder particles into a ball milling tank of a ball mill, and ball milling for 8 hours under the protection of high-purity argon; s4, putting the mixed powder particles subjected to ball milling in the S3 mode into a die for isostatic pressing, wherein the pressure is 250 Mpa; s5, sintering the blank obtained after isostatic cool pressing in a high-purity argon protective atmosphere at the sintering temperature of 950 ℃ for 8 hours; s6, secondary repressing pressure 500 Mpa; s7, sintering the pressed blank for the second time in the protective atmosphere of high-purity hydrogen at the sintering temperature of 950 ℃ for 6 hours; s8, carrying out hot extrusion on the obtained blank under the protection of high-purity hydrogen, wherein the hot extrusion temperature is 850 ℃, the extrusion ratio is 100: 1, extrusion speed of 3cm/min and extrusion die preheating temperature of 500 ℃. Finally, the graphene molybdenum electrical contact material is prepared. Compared with the traditional silver-based electrical contact material, the silver-saving effect is 98%.
Experiments prove that the electric contact adopting the graphene material containing 98% can greatly reduce the production cost, ensure that the electric contact has better electric conductivity which can reach 37.2MS/m, and still have good wear resistance and thermal conductivity.
Compared with the silver-based electrical contact material, the graphene-based silver-saving electrical contact material does not contain or contains a small amount of silver, and fully utilizes the graphene as the matrix material to replace the silver, which is completely different from the method that other metals are adopted as the matrix material and only a small amount of graphene material is added in the matrix material in the prior art. The graphene-based silver-saving electrical contact material manufactured by the method has the advantages of reducing the contact resistance, improving the conductivity and reducing the cutting action of the additive on the matrix, wherein the metal-coated powder particles generated by plasma sputtering deposition improve the easy agglomeration and uneven distribution of the graphene, the interface bonding force and wettability between the graphene and the additive, reduce the cutting action of the additive on the matrix, and are beneficial to obtaining good interface bonding, so that the conductivity, the heat conduction performance and the arc erosion resistance of the graphene-based silver-saving electrical contact material are improved, and the processing performance of the graphene-based silver-saving electrical contact material is effectively improved. The capability of fusion welding resistance and electric arc burning resistance and mechanical performance are improved, silver is greatly saved, the manufacturing cost can be obviously reduced, and the method is suitable for large-scale production.
Claims (10)
1. The graphene-based silver-saving electrical contact material is characterized by comprising 10.1-98 wt% of graphene and an additive, wherein the additive comprises Au, Ag, Cu, Ti, CdO and SnO2One or more of ZnO, NI, Zr, W, Mo, V, Nb, Ta, rare earth metals and graphite or alloys and compounds thereof.
2. The graphene-based silver-saving electrical contact material according to claim 1, wherein the graphene and the additive are in the form of powder particles, the purity of the additive powder is 99.99%, the particle size of the additive powder is 3nm-3 μm, and the graphene and the additive powder particles are coated with metal.
3. The graphene-based silver-saving electrical contact material according to claim 1, wherein graphene is an N layer, and N is 1-10.
4. A method for preparing the graphene-based silver-saving electrical contact material as claimed in any one of claims 1 to 2, wherein:
s1, cleaning the metal target material, immersing the target material in dilute sulfuric acid, taking out after immersing for a period of time, washing with deionized water, washing with acetone and drying, wherein the purity of the target material is 99.99%;
s2, fixing the clean target material on a target frame of a high-power pulse magnetron plasma sputtering instrument;
s3, vacuumizing the plasma sputtering instrument, and starting a heater to reach the temperature of 300-500 ℃ when the vacuum degree of a cavity of the plasma sputtering instrument reaches a preset value, wherein the rotating speed of the workpiece frame is 5-8 rpm;
s4, sputtering target materials by using a plasma sputtering instrument, and respectively generating metal-coated powder particles on the graphene and the additive powder;
s5, putting the graphene prepared in the S4 and the metal-coated powder particles of the additive into a ball milling tank of a ball milling powder mixer, introducing argon, and mixing the powder for 8-12 hours under the protection of high-purity argon atmosphere;
s6, performing isostatic pressing preforming on the mixed metal-coated powder particles at a forming pressure of 150-300 mPa to preform an extrusion blank;
s7, sintering the extrusion blank under the protection of high-purity argon or hydrogen gas, and then preserving heat;
s8, carrying out hot extrusion deformation on the sintered blank;
s9, preserving the heat of the extruded and deformed blank for 1.5h, and cooling to 350 ℃;
s10: the graphene-based silver-saving electrical contact material is prepared through the working procedures of rolling, drawing and the like.
5. The method for preparing the graphene-based silver-saving electrical contact material according to claim 4, wherein in the step S1, the dilute sulfuric acid is soaked for 5-10 minutes at a concentration of 10-30%.
6. The method for preparing the graphene-based silver-saving electrical contact material according to claim 4, wherein in step S4, high-purity argon gas is introduced into a cavity of a plasma sputtering instrument, when the vacuum degree is 0.3-0.9 Pa, a plasma sputtering power supply is started, the bias voltage is adjusted to 600-1000V, and sputtering is carried out for 5-60 minutes.
7. The method for preparing the graphene-based silver-saving electrical contact material as claimed in claim 4, wherein in the step S7, the sintering temperature is 750-.
8. The method for preparing the graphene-based silver-saving electrical contact material as claimed in claim 4, wherein in the step S8, the extrusion temperature is 650- > 950 ℃, and the extrusion ratio is (50-200): 1.
9. the method for preparing the graphene-based silver-saving electrical contact material according to claim 4, wherein the purity of the high-purity argon (or hydrogen) is 99.99%.
10. The method of claim 4, wherein the metal target comprises Au, Ag, Cu, Ti, Cd, Sn, Zn, NI, Zr, W, Mo, V, Nb, Ta, rare earth metals with a purity of 99.99%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115446307A (en) * | 2022-09-22 | 2022-12-09 | 长沙升华微电子材料有限公司 | Preparation method of graphene-copper composite material |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105428097A (en) * | 2015-12-24 | 2016-03-23 | 济南大学 | Silver-based electrical contact composite material and preparation method therefor |
| CN105551860A (en) * | 2016-02-26 | 2016-05-04 | 济南大学 | Preparation method of nickel-plated graphene/silver-nickel electrical contact material |
| CN105679560A (en) * | 2016-02-26 | 2016-06-15 | 济南大学 | Preparation method of nickel-plated graphene-reinforced silver-based electrical contact material |
| CN105810292A (en) * | 2016-04-29 | 2016-07-27 | 无锡光富光伏材料有限公司 | Graphene silver paste and preparation method and application thereof |
| CN105838914A (en) * | 2016-04-16 | 2016-08-10 | 苏州思创源博电子科技有限公司 | Preparation method of silver-based contact material containing graphene |
| CN106086503A (en) * | 2016-07-20 | 2016-11-09 | 浙江大学 | A kind of high connductivity flexibility silver-based composite material and preparation method thereof |
| WO2017008716A1 (en) * | 2015-07-13 | 2017-01-19 | 严利容 | New type of silver-based low-voltage contact material and method for fabrication thereof |
| CN108330312A (en) * | 2018-03-06 | 2018-07-27 | 昆明理工大学 | A kind of preparation method of the graphene reinforced metal-matrix composite of metallic cover |
| CN109365799A (en) * | 2018-09-19 | 2019-02-22 | 上海新池能源科技有限公司 | Preparation method and Metal Substrate-graphene electric contact of graphene coated metal-powder |
| CN109518029A (en) * | 2018-12-19 | 2019-03-26 | 昆明理工大学 | A kind of preparation method of Ag- graphene contact material |
-
2021
- 2021-09-03 CN CN202111035729.9A patent/CN114101666B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017008716A1 (en) * | 2015-07-13 | 2017-01-19 | 严利容 | New type of silver-based low-voltage contact material and method for fabrication thereof |
| CN105428097A (en) * | 2015-12-24 | 2016-03-23 | 济南大学 | Silver-based electrical contact composite material and preparation method therefor |
| CN105551860A (en) * | 2016-02-26 | 2016-05-04 | 济南大学 | Preparation method of nickel-plated graphene/silver-nickel electrical contact material |
| CN105679560A (en) * | 2016-02-26 | 2016-06-15 | 济南大学 | Preparation method of nickel-plated graphene-reinforced silver-based electrical contact material |
| CN105838914A (en) * | 2016-04-16 | 2016-08-10 | 苏州思创源博电子科技有限公司 | Preparation method of silver-based contact material containing graphene |
| CN105810292A (en) * | 2016-04-29 | 2016-07-27 | 无锡光富光伏材料有限公司 | Graphene silver paste and preparation method and application thereof |
| CN106086503A (en) * | 2016-07-20 | 2016-11-09 | 浙江大学 | A kind of high connductivity flexibility silver-based composite material and preparation method thereof |
| CN108330312A (en) * | 2018-03-06 | 2018-07-27 | 昆明理工大学 | A kind of preparation method of the graphene reinforced metal-matrix composite of metallic cover |
| CN109365799A (en) * | 2018-09-19 | 2019-02-22 | 上海新池能源科技有限公司 | Preparation method and Metal Substrate-graphene electric contact of graphene coated metal-powder |
| CN109518029A (en) * | 2018-12-19 | 2019-03-26 | 昆明理工大学 | A kind of preparation method of Ag- graphene contact material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115446307A (en) * | 2022-09-22 | 2022-12-09 | 长沙升华微电子材料有限公司 | Preparation method of graphene-copper composite material |
| CN115446307B (en) * | 2022-09-22 | 2023-08-18 | 长沙升华微电子材料有限公司 | Preparation method of graphene copper composite material |
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