CN112151285A - Two-dimensional lamellar phase enhanced silver-based electric contact material and preparation method thereof - Google Patents
Two-dimensional lamellar phase enhanced silver-based electric contact material and preparation method thereof Download PDFInfo
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- CN112151285A CN112151285A CN202010922256.3A CN202010922256A CN112151285A CN 112151285 A CN112151285 A CN 112151285A CN 202010922256 A CN202010922256 A CN 202010922256A CN 112151285 A CN112151285 A CN 112151285A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0233—Composite material having a noble metal as the basic material and containing carbides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
- H01H1/023—Composite material having a noble metal as the basic material
- H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
- H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
Abstract
The invention discloses a two-dimensional lamellar phase reinforced silver-based electric contact material and a preparation method thereof, and relates to the technical field of metal-based composite materials. Compared with metallic silver, the silver-based electric contact material obtained by the method has the advantages that the hardness is improved, and the resistivity change is small.
Description
The technical field is as follows:
the invention relates to the technical field of metal-based composite materials, in particular to a two-dimensional lamellar phase enhanced silver-based electric contact material and a preparation method thereof.
Background art:
according to relevant statistics, the market size of the global electrical contact material reaches $ 36.3 billion in 2017, and is expected to reach $ 59.38 billion in 2025, and the annual composite growth rate (CAGR) is 6.34%, namely the electrical contact material has great market demand and bright future. The working environment of the electric contact material determines that the electric contact material has good electric conduction and thermal conductivity, good processing performance, certain strength and other properties, and the metal silver has excellent electric conduction and thermal conductivity, processing performance and oxidation resistance and is widely applied to preparation of various electric contact materials such as relays, contactors, load switches and the like. Although the metallic silver has extremely low contact resistance, the performance defects (such as low hardness, poor wear resistance and the like) of the metallic silver cause the metallic silver to be compounded with other materials so as to improve the performance of the metallic silver.
Two-dimensional materials have attracted considerable attention since their advent, and particular structures have given them superior properties. The graphene and the metal carbide or nitride material (Mxene material) with the two-dimensional layered structure are taken as a typical two-dimensional material, have excellent mechanical properties, can optimize the normal-temperature mechanical properties such as strength, hardness and the like of a matrix and high-temperature properties when added into metal, and can be used as a reinforcing phase of an electric contact material.
Patent CN 105575684a discloses a silver-based electrical contact composite material, which is prepared by mixing graphene and silver powder through ball milling and then sintering. Patent CN 107146650a discloses an Ag-MXene contact material, which is prepared by mixing silver and MXene through wet mixing and sintering. Although the hardness of the silver is improved by introducing the two-dimensional lamellar reinforcing phase, the interface of the matrix and the reinforcing phase cannot be uniformly and tightly combined due to direct mixing, the improvement on the comprehensive performance of the composite material is limited, for example, the conductivity of the contact material in CN 105575684A can be maintained, but the hardness value is only 52HB at most. The electrical resistivity of the contact material of CN 107146650A is 16 multiplied by 10-3Mu omega, m is increased to (27-33) × 10-3Mu omega, m, increased by 69-106%.
In order to improve the interface bonding effect between a matrix and a reinforcing phase, patent CN 102385938A discloses a metal-based graphene composite electrical contact material and a preparation method thereof, which comprises forming a metal precipitation layer on the surface of graphene by a precipitation method, and then mixing the graphene containing the precipitation layer with metal powder. Although the interface bonding effect of the graphene and the metal powder is improved to a certain extent, due to the problem that the graphene and the metal precipitation layer are poor in wetting, the heat conductivity of the obtained composite electric contact material is still insufficient, so that the heat of the electric contact cannot be timely transmitted, and large burning loss is generated in a small breaking frequency in a quick switch test. And because hydrazine hydrate is used in the precipitation process, the substance has high toxicity and is not beneficial to industrial production.
The invention content is as follows:
the invention aims to provide a two-dimensional lamellar phase reinforced silver-based electric contact material and a preparation method thereof, the electric contact material is obtained by taking graphene or MXene with a surface rich in functional groups as a reinforcing phase and depositing silver on the surface, and the electric contact material has high hardness and small resistivity, and is relatively less dangerous because hydrazine hydrate is not used in the preparation process.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the two-dimensional lamellar phase reinforced silver-based electric contact material comprises a matrix phase and a reinforcing phase, wherein the matrix phase is silver, the reinforcing phase is a two-dimensional lamellar structure with a surface rich in functional groups, and silver precipitates are coated on the surface of the reinforcing phase.
The functional group includes an oxygen-containing functional group.
The reinforcement phase includes reduced graphene oxide (rGO) and/or MXene.
The MXene comprises Ti3C2、Ti2C、Ta4C3、(Ti0.5Nb0.5)2C、Ti3CN and Mo2C.
The mass fraction of the matrix phase in the silver-based electric contact material is 90-99.9%, and the mass fraction of the reinforcing phase is 0.1-10%.
The preparation method of the two-dimensional lamellar phase reinforced silver-based electric contact material comprises the following specific steps:
(1) mixing a two-dimensional lamellar material with a surface rich in functional groups with silver salt to obtain a solution A;
(2) adding a precipitator into the solution A to enable silver ions to form precipitates and coat the precipitates on the surface of the two-dimensional sheet material;
(3) and washing, drying and carrying out heat treatment in an oxygen-free atmosphere to obtain the silver-based electric contact material.
The two-dimensional sheet material comprises a graphene oxide suspension rich in a large number of functional groups and/or an MXene suspension rich in a large number of functional groups.
The graphene oxide suspension is prepared by strong acid oxidation treatment through a Brodie method, a Staudenmaier method or a Hummers method.
The MXene suspension is prepared by acid liquor etching or intercalation etching of acid liquor and lithium fluoride.
The silver salt is soluble salt, preferably one or more of silver nitrate and silver sulfate solution, and the concentration of the silver salt solution is 0.01-0.5 mol per liter.
In order to make the large number of functional groups carried on the two-dimensional lamellar reinforcing phase and silver ions be adsorbed and self-assembled better, the mixing of the step (1) comprises one or more of but is not limited to magnetic stirring, mechanical stirring and ultrasonic mixing.
In order to facilitate impurity removal, the precipitating agent comprises one or more of sodium carbonate and sodium hydroxide, the concentration of the precipitating agent is 0.01-0.5 mol/L, and enough precipitating agent is added to completely precipitate silver ions. In order to make the precipitation more uniform, the precipitant addition rate is < 5 mL/min.
The washing liquid adopted by washing is deionized water and absolute ethyl alcohol, and the washing times are 2-3; the drying condition is vacuum drying at 30-80 ℃ for 2-24 h.
The heat treatment comprises one or more of powder metallurgy, plasma spark sintering and microwave sintering, wherein the sintering atmosphere comprises vacuum or at least one of nitrogen, hydrogen and argon, the sintering temperature is 650-900 ℃, and the sintering time is 2-5 h.
For convenience of testing or use, the powder dried in step (3) may be compressed into tablets and then subjected to heat treatment, and the conditions for compression into tablets are as follows: tabletting at 400-600MPa and maintaining the pressure for 60-180s, and molding.
The invention has the beneficial effects that:
(1) the invention adopts the two-dimensional lamellar with rich functional groups on the surface as the reinforcing phase, and because the surface functional groups have polarity, silver ions are coated on the matrix in a self-assembly and precipitation way through electrostatic adsorption, so that the matrix and the reinforcing phase can achieve molecular level mixing, and the wetting effect of two phases at the interface is better. Compared with metallic silver, the silver-based electric contact material obtained by the method has the advantages that the hardness and the heat-conducting property are improved, and the resistivity change is small.
(2) The invention realizes coating by metal ion precipitation, and does not relate to substances with higher toxicity, such as hydrazine hydrate, thereby being beneficial to industrial production.
Description of the drawings:
FIG. 1 is an electron micrograph of a precipitate according to example 1 of the present invention;
FIG. 2 is an electron micrograph of a precipitate according to example 4 of the present invention;
FIG. 3 is an electron micrograph of a precipitate according to a comparative example of the present invention.
The specific implementation mode is as follows:
in order to make the technical means, the original characteristics, the achieved purposes and the effects of the invention easy to understand, the invention is further explained by combining the specific embodiments and the drawings.
Example 1
(1) Preparing graphite oxide by using a Hummers method by using flaky graphite as a raw material, and then carrying out ultrasonic treatment for 10 hours by using an ultrasonic machine to obtain a well-dispersed 0.5mg/mL graphene oxide solution.
(2) 3.3974g of silver nitrate is added into 9.31mL of graphene oxide solution, then deionized water is added to 100mL, ultrasonic mixing is carried out at low temperature, mechanical stirring is carried out for 30min, and electrostatic adsorption self-assembly is completed.
(3) Adding 100mL of water into 0.88g of sodium hydroxide, uniformly stirring, and dripping the mixed salt solution at the speed of 3mL/min under the mechanical stirring of 800r/min in the whole process.
(4) And washing and filtering the precipitate for 3 times, drying the precipitate at 50 ℃ in vacuum for 12 hours, grinding the composite material powder, maintaining the pressure at 550MPa for 90s, tabletting, and sintering in a vacuum furnace, wherein the sintering parameter is 750 ℃, and keeping the temperature for 3 hours to obtain the silver-based electrical contact material.
Example 2
(1) Preparing graphite oxide by using a Hummers method by using flaky graphite as a raw material, and then carrying out ultrasonic treatment for 10 hours by using an ultrasonic machine to obtain a well-dispersed 5mg/mL graphene oxide solution.
(2) 3.3974g of silver nitrate is added into 37.52mL of graphene oxide solution, then deionized water is added into the solution to 100mL, ultrasonic mixing is carried out at low temperature, mechanical stirring is carried out for 30min, and electrostatic adsorption self-assembly is completed.
(3) Adding 0.88g of sodium hydroxide into 100mL of water, uniformly stirring, and dripping the mixed salt solution at the speed of 4mL/min under mechanical stirring at 750r/min in the whole process.
(4) And washing and filtering the precipitate for 3 times, then drying the precipitate at 50 ℃ in vacuum for 12h, grinding the composite material powder, maintaining the pressure at 550MPa for 90s, tabletting, then placing the powder in a nitrogen atmosphere for sintering, and keeping the sintering parameter at 850 ℃ for 3h to obtain the silver-based electrical contact material.
Example 3
(1) Preparing graphite oxide by using a Hummers method by using flaky graphite as a raw material, and then carrying out ultrasonic treatment for 10 hours by using an ultrasonic machine to obtain a well-dispersed 5mg/mL graphene oxide solution.
(2) 1.6987g of silver nitrate is added into 6.62mL of graphene oxide solution, then deionized water is added to 100mL, ultrasonic mixing is carried out at low temperature, mechanical stirring is carried out for 30min, and electrostatic adsorption self-assembly is completed.
(3) Adding 0.44g of sodium hydroxide into 100mL of water, uniformly stirring, and dripping the mixed salt solution at the speed of 3mL/min under mechanical stirring of 750r/min in the whole process.
(4) And washing and filtering the precipitate for 3 times, drying the precipitate for 12h at 50 ℃ in vacuum, grinding the composite material powder, maintaining the pressure at 550MPa for 90s, tabletting, and sintering in a vacuum furnace, wherein the sintering parameter is 750 ℃, and keeping the temperature for 3h to obtain the silver-based electrical contact material.
Example 4
(1) Etching Ti using LiF and HF3AlC2Centrifugally washing to neutrality to obtain Ti containing a large number of functional groups3C2Obtaining 1mg/mL Ti with good dispersion after argon protection and ultrasound3C2And (3) solution.
(2) 3.3974g of silver nitrate was added to 20.20mL of Ti3C2And adding deionized water to 100mL after the solution is dissolved, ultrasonically mixing and mechanically stirring for 30min to finish electrostatic adsorption self-assembly.
(3) Adding 100mL of water into 0.88g of sodium hydroxide, uniformly stirring, and dripping the mixed salt solution at the speed of 3mL/min under the mechanical stirring of 800r/min in the whole process.
(4) And washing and filtering the precipitate for 3 times, drying the precipitate at 50 ℃ in vacuum for 12h, grinding the composite material powder, maintaining the pressure at 550MPa for 90s, tabletting, and sintering in a vacuum furnace, wherein the sintering parameter is 700 ℃ and the temperature is kept for 3h to obtain the silver-based electrical contact material.
Comparative example 1
(1) 3.3974g of silver nitrate and 0.88g of sodium hydroxide are respectively added into 100mL of deionized water and stirred uniformly, the sodium hydroxide is dripped into the silver nitrate solution at the dripping speed of 3mL/min, and mechanical stirring is assisted by 800r/min in the whole process.
(2) Washing and filtering the precipitate for 3 times, drying the precipitate at 50 ℃ in vacuum for 12h, grinding the composite material powder, maintaining the pressure at 550MPa for 90s, tabletting, placing the obtained product in a vacuum furnace, sintering, keeping the sintering parameter at 400 ℃ for 1h, and keeping the temperature at 750 ℃ for 3h to obtain the silver-based electrical contact material.
Comparative example 2
The electrical contact material obtained in comparative example 2 was 38.2MS/m in terms of electrical conductivity and 2.84X 10 in terms of resistivity, wherein example 2 of CN 102385938A was used as comparative example 27μΩ·m。
As can be seen by comparing fig. 1, 2 and 3, when a two-dimensional lamellar enhanced phase is introduced, silver ions in both fig. 1 and 2 precipitate around the lamellar enhanced phase.
TABLE 1 hardness, resistivity, and thermal conductivity of the materials prepared in the examples and comparative examples
The hardness and resistivity data in the table 1 are obtained by testing according to the GB/T5586-2016 electric contact material basic performance test method. As can be seen from Table 1, when the two-dimensional lamellar reinforcing phase is introduced, the hardness of the matrix metal silver is improved, the service life of the matrix metal silver is prolonged, and compared with the prior art, the two-dimensional lamellar reinforcing phase has the advantages that the hardness is improved while the same level of conductivity is kept. The reinforcing phase is introduced by the method, so that the loss of electrical properties is small and is close to the resistivity of pure silver. As can be seen from the thermal conductivity of example 3 and comparative example 2, the thermal conductivity of example 3 is greater than that of comparative example 2 at the same graphene content.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (13)
1. A two-dimensional lamellar phase enhanced silver-based electrical contact material, characterized in that: the silver-based composite material comprises a matrix phase and a reinforcing phase, wherein the matrix phase is silver, the reinforcing phase is a two-dimensional lamellar structure with a surface rich in functional groups, and silver precipitates are coated on the surface of the reinforcing phase.
2. The two-dimensional lamellar phase-strengthened silver-based electrical contact material according to claim 1, characterized in that: the functional group includes an oxygen-containing functional group.
3. The two-dimensional lamellar phase-strengthened silver-based electrical contact material according to claim 1, characterized in that: the reinforcement phase includes reduced graphene oxide (rGO) and/or MXene.
4. The two-dimensional lamellar phase-strengthened silver-based electrical contact material according to claim 3, characterized in that: the MXene comprises Ti3C2、Ti2C、Ta4C3、(Ti0.5Nb0.5)2C、Ti3CN and Mo2C.
5. The two-dimensional lamellar phase-strengthened silver-based electrical contact material according to claim 1, characterized in that: the mass fraction of the matrix phase in the silver-based electric contact material is 90-99.9%, and the mass fraction of the reinforcing phase is 0.1-10%.
6. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to any of claims 1 to 5, characterized in that: the method comprises the following specific steps:
(1) mixing a two-dimensional lamellar material with a surface rich in functional groups with silver salt to obtain a solution A;
(2) adding a precipitator into the solution A to enable silver ions to form precipitates and coat the precipitates on the surface of the two-dimensional sheet material;
(3) and washing, drying and carrying out heat treatment in an oxygen-free atmosphere to obtain the silver-based electric contact material.
7. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to claim 6, characterized in that: the two-dimensional sheet material comprises a graphene oxide suspension rich in a large number of functional groups and/or an MXene suspension rich in a large number of functional groups.
8. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to claim 7, characterized in that: the graphene oxide suspension is prepared by strong acid oxidation treatment through a Brodie method, a Staudenmaier method or a Hummers method; the MXene suspension is prepared by acid liquor etching or intercalation etching of acid liquor and lithium fluoride.
9. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to claim 6, characterized in that: the silver salt is soluble salt, preferably one or more of silver nitrate and silver sulfate solution, and the concentration of the silver salt solution is 0.01-0.5 mol per liter.
10. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to claim 6, characterized in that: the precipitant comprises one or more of sodium carbonate and sodium hydroxide, the concentration of the precipitant is 0.01-0.5 mol/L, and the dripping speed of the precipitant is less than 5 mL/min.
11. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to claim 6, characterized in that: the washing liquid adopted by washing is deionized water and absolute ethyl alcohol, and the washing times are 2-3; the drying condition is vacuum drying at 30-80 ℃ for 2-24 h.
12. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to claim 6, characterized in that: the heat treatment comprises one or more of powder metallurgy, plasma spark sintering and microwave sintering, wherein the sintering atmosphere comprises vacuum or at least one of nitrogen, hydrogen and argon, the sintering temperature is 650-900 ℃, and the sintering time is 2-5 h.
13. The method for preparing a two-dimensional lamellar phase-reinforced silver-based electrical contact material according to claim 6, characterized in that: the powder dried in the step (3) can be pressed into tablets and then subjected to heat treatment, and the conditions for pressing into tablets are as follows: tabletting at 400-600MPa and maintaining the pressure for 60-180s, and molding.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102385938A (en) * | 2011-11-10 | 2012-03-21 | 电子科技大学 | Metal matrix graphene composite electrical contact material and preparation method thereof |
| CN103233136A (en) * | 2013-04-26 | 2013-08-07 | 河北工业大学 | Technology for preparing silver rare earth oxide electric contact material for low voltage electric apparatus with liquid phase method |
| CN104148663A (en) * | 2014-07-15 | 2014-11-19 | 东南大学 | Method for efficiently preparing silver nano particle-graphene three-dimensional composite structure |
| CN104700961A (en) * | 2015-03-18 | 2015-06-10 | 上海和伍新材料科技有限公司 | Graphene/silver composite material and preparation method thereof |
| CN107761081A (en) * | 2017-09-27 | 2018-03-06 | 郴州博太超细石墨股份有限公司 | A kind of graphene/silver composite material of high-compactness and preparation method thereof |
| CN108677048A (en) * | 2018-04-20 | 2018-10-19 | 西安理工大学 | A kind of silver-based composite material of nitrogen-doped graphene and preparation method thereof |
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- 2020-09-04 CN CN202010922256.3A patent/CN112151285B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102385938A (en) * | 2011-11-10 | 2012-03-21 | 电子科技大学 | Metal matrix graphene composite electrical contact material and preparation method thereof |
| CN103233136A (en) * | 2013-04-26 | 2013-08-07 | 河北工业大学 | Technology for preparing silver rare earth oxide electric contact material for low voltage electric apparatus with liquid phase method |
| CN104148663A (en) * | 2014-07-15 | 2014-11-19 | 东南大学 | Method for efficiently preparing silver nano particle-graphene three-dimensional composite structure |
| CN104700961A (en) * | 2015-03-18 | 2015-06-10 | 上海和伍新材料科技有限公司 | Graphene/silver composite material and preparation method thereof |
| US20180073105A1 (en) * | 2015-03-18 | 2018-03-15 | Shanghai Hiwave Composite Materials Co., Ltd. | Gaphene/silver composite material and preparation method thereof |
| CN107761081A (en) * | 2017-09-27 | 2018-03-06 | 郴州博太超细石墨股份有限公司 | A kind of graphene/silver composite material of high-compactness and preparation method thereof |
| CN108677048A (en) * | 2018-04-20 | 2018-10-19 | 西安理工大学 | A kind of silver-based composite material of nitrogen-doped graphene and preparation method thereof |
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