CN106086503B - A kind of highly conductive flexible silver-based composite material and preparation method thereof - Google Patents
A kind of highly conductive flexible silver-based composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C5/00—Alloys based on noble metals
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- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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Abstract
The present invention relates to metal-base composites technology, it is desirable to provide a kind of highly conductive flexible silver-based composite material and preparation method thereof.Following components that its composition of raw materials is calculated by weight form：Silver powder 75~85%, graphene powder 0.5~12%, nano-nickel collosol 5 14.5%, diboron trioxide powder 1 2.5%, zirconium dioxide powder 0.5 2%, dispersant 0.5~1%.The present invention utilizes the characteristics such as graphene high electron mobility, high Young's modulus and excellent deformation performance, with reference to the excellent mechanical performance of zirconium dioxide and the sintering characteristic of diboron trioxide, it is modified by nano-nickel collosol, so as to obtain high conductivity, high-elongation, high-tensile highly conductive flexible silver-based composite material, the deficiencies of high existing environment-friendly silver base electrical contact material resistivity, processability difference can be improved, and resistance to arc erosion, there is long electric life.Preparation technology of the invention is simple, process is environmentally friendly, high yield rate, can largely save the dosage of noble silver, reduce production cost.
Description
Technical field
The invention belongs to metal-base composites technical field, and in particular to a kind of highly conductive flexible silver-based composite material and
Its preparation method.
Background technology
Silver-based composite material has excellent electric conductivity, thermal conductivity, ductility and machining property, is optimal lead
One of electric class material, has important strategic position in fields such as Aero-Space, track traffic, power electronics.Wherein, make electrical contact with
The key foundation of material and component as electrical equipment industry, it is one of most important application field of silver base conductive material.AgCdO is answered
Condensation material has resistance to electric arc, anti-melting welding, resistance to electrically and mechanically abrasion, corrosion-resistant and low contact resistance and good processability etc.
Advantage, in larger operating voltage or current range, excellent electrical contact performance is all shown, be referred to as " omnipotent contact material
Material ".From the 1950s so far, Ag/CdO conducing composite materials are always in occupation of the leading of silver-based electric contact material market.
However, AgCdO, as contact material, it can cause certain journey to human body and environment in the production and use process
The harm of degree.European Union promulgates within 2 months 2003《On prohibitting the use of some Hazardous Substances Directives in electronic and electrical equipment》
(RoHS instructions) and《Waste and old electric electrical equipment》(WEEE instructions), is limited the application containing cadmium material in electronic and electrical equipment,
The research boom of novel environment friendly contact material is started.And in the contact material product that China produces and sells, AgCdO
The share of material still accounts for more than half so far, and this greatly limits the development of China's contact material and its downstream industry.Closely
Over 10 years, researcher has carried out substantial amounts of research work around environment-friendly type without cadmium electric contact composite material, is concentrated mainly on new
Material system is explored, has the modification of material system and the control of composite structure etc., it has also become silver-based compound electric
The trend of contact material research and development.
However, more Ag/SnO is studied and applied at present2, the environment-friendly type contact material such as Ag/ZnO, although mechanics, electricity
Etc. performance is relatively excellent, can meet use demand within the specific limits, but due to SnO2, the enhancing phase such as ZnO electrical conductivity
With silver compared to still poor several orders of magnitude so that silver-based composite material still can not meet high conductivity, high mechanical properties requirement
Application field demand.Particularly when silver content is reduced to below 90wt% in composite, not only electrical conductivity is difficult to protect
Card, while composite processing performance can also be deteriorated with the reduction of silver content, so as to cause product combination property to decline, apply
Limited, there is also the skill for the problems such as decrease in yield, production cost increase, being the current application of environment-friendly type contact material and development
Art bottleneck.Therefore, exploitation high conductivity, the environment-friendly type silver-based that processability is excellent, silver content is low, production cost is relatively low are needed badly
Contact material.
Graphene has exceeded in other metallic monomers or semiconductor as a kind of new carbon, its electronic movement velocity
In movement velocity, the 1/300 of the light velocity can be reached, the electron mobility on graphene planes is up to 2 × 10 at room temperature5cm2·V-1·s-1.The Young's modulus of single-layer graphene is up to 1100GPa, and toughness is very good, can arbitrarily bend.Therefore, by stone
Black alkene is expected to improve the problems such as existing environment-friendly silver base electrical contact material electrical conductivity is low, processability is poor as enhancing phase.
The content of the invention
The technical problems to be solved by the invention are to overcome above deficiency of the prior art, there is provided a kind of highly conductive soft
Property silver-based composite material and preparation method thereof.When the silver-based composite material that this method prepares is used as contact material, in silver
In the case that content is relatively low, the excellent specific property still with high conductivity, high deflection, and tensile strength is high, resistance to arc erosion, tool
There is long electric life.
In order to solve the above technical problems, the solution of the present invention is：
A kind of composition of raw materials of highly conductive flexible silver-based composite material is provided, is following groups calculated by weight
It is grouped into：Silver powder 75~85%, graphene powder 0.5~12%, nano-nickel collosol 5-14.5%, diboron trioxide powder 1-
2.5%, zirconium dioxide powder 0.5-2%, dispersant 0.5~1%.
In the present invention, the dispersant is potassium carboxymethylcellulose.
Invention further provides the method for preparing highly conductive flexible silver-based composite material using aforementioned base materials formula, bag
Include following step：
(1) each component is weighed by the proportionate relationship of the composition of raw materials；
(2) nano-nickel collosol is placed in stirring ball-milling equipment, graphene is added while stirring under 1200r/min speed
Powder, 40min is sufficiently mixed, obtains compound slurry A；Compound slurry A is placed in ultrasonic device and is ultrasonically treated 1-2h, it is standby；
(3) by load weighted diboron trioxide powder, zirconium dioxide powder, the silver powder and deionization for accounting for silver powder total amount 20%
Water is mixed, and adds dispersant, and the compound slurry B that concentration is 20-30wt% is configured under 2000r/min mixing speed；
(4) compound slurry A and compound slurry B are placed in reactor, 1-2h is reacted under the conditions of 80-160 DEG C, is answered
Slurry C is closed, it is standby；
(5) compound slurry C is placed in mechanical stirring equipment, added while stirring under 1000r/min speed remaining
Silver powder, obtain compound slurry D；
(6) by the spray-dried rear acquisition silver-based composite granules of compound slurry D；
(7) silver-based composite granule is placed in mould, the cold isostatic compaction under 200MPa pressure, obtains silver-based composite wood
Expect biscuit；
(8) silver-based composite material biscuit is placed in sintering furnace, 2~4 is sintered under the conditions of air atmosphere, 800~900 DEG C
Hour, obtain highly conductive flexible silver-based composite material.
In the present invention, the particle diameter of the silver powder is 0.5~2um, purity 99.99%.
In the present invention, the number of plies of the graphene powder is 1-10 atomic layer, and lamella size is 0.05-50um.
In the present invention, the nano-nickel collosol, particle diameter 30-100nm, concentration 5-20wt%.
In the present invention, the diboron trioxide powder is pure to analyze.
In the present invention, the particle diameter of the zirconium dioxide powder is 0.5-1 μm, purity 99%.
In the present invention, in the step (2), the frequency of ultrasonic device is 50HZ.
Inventive principle explanation：
In the preparation method of the present invention, step (2) is to form the key of continuous conductive microstructure passage, and step (3) is to be formed
Continuous conduction strengthens the basis of phase, with reference to step (4) and step (5), can collectively form to have in silver-based composite material and lead
The composite network structure of electricity and enhancing effect, so as to obtain with excellent properties such as high conductivity, high-elongation, high-tensiles
Highly conductive flexible silver-based composite material.
Compared with prior art, the beneficial effects of the present invention are：
1st, the present invention utilizes the characteristics such as graphene high electron mobility, high Young's modulus and excellent deformation performance, with reference to
The sintering characteristic of the excellent mechanical performance of zirconium dioxide and diboron trioxide, is modified by nano-nickel collosol, so as to obtain high electricity
Conductance, high-elongation, the highly conductive flexible silver-based composite material of high-tensile, can improve existing environment-friendly type silver-based electric contact
The deficiencies of resistivity of material is high, processability difference, and resistance to arc erosion, have long electric life.
2nd, preparation technology of the invention is simple, process is environmentally friendly, high yield rate, can largely save the dosage of noble silver,
Reduce production cost.
Embodiment
Below by example, the present invention is further described.
In the present invention, a kind of composition of raw materials of highly conductive flexible silver-based composite material, is calculated by weight
Following component compositions：Silver powder 75~85%, graphene powder 0.5~12%, nano-nickel collosol 5-14.5%, diboron trioxide powder
Body 1-2.5%, zirconium dioxide powder 0.5-2%, dispersant 0.5~1%.
The method that highly conductive flexible silver-based composite material is prepared using the composition of raw materials, is comprised the steps：
(1) each component is weighed by the proportionate relationship of the composition of raw materials；
(2) nano-nickel collosol is placed in stirring ball-milling equipment, graphene is added while stirring under 1200r/min speed
Powder, 40min is sufficiently mixed, obtains compound slurry A；Compound slurry A is placed in ultrasonic device and is ultrasonically treated 1-2h, it is standby；
(3) by load weighted diboron trioxide powder, zirconium dioxide powder, the silver powder and deionization for accounting for silver powder total amount 20%
Water is mixed, and adds dispersant, and the compound slurry B that concentration is 20-30wt% is configured under 2000r/min mixing speed；
(4) compound slurry A and compound slurry B are placed in reactor, 1-2h is reacted under the conditions of 80-160 DEG C, is answered
Slurry C is closed, it is standby；
(5) compound slurry C is placed in mechanical stirring equipment, added while stirring under 1000r/min speed remaining
Silver powder, obtain compound slurry D；
(6) by the spray-dried rear acquisition silver-based composite granules of compound slurry D；
(7) silver-based composite granule is placed in mould, the cold isostatic compaction under 200MPa pressure, obtains silver-based composite wood
Expect biscuit；
(7) silver-based composite material biscuit is placed in sintering furnace, 2~4 is sintered under the conditions of air atmosphere, 800~900 DEG C
Hour, obtain highly conductive flexible silver-based composite material.
Test data in each embodiment see the table below (number of each component is weight percent content)：
It is and existing when the highly conductive flexible silver-based composite material prepared using the inventive method is used as contact material
Silver content identical contact material is compared in technology, and its resistivity substantially reduces, and elongation percentage significantly improves, and tensile strength carries
It is high.
For example, silver mass fraction is 88% AgSnO in commercially available prod2Material, its resistivity are generally 2.2~2.5 μ
Ω cm, elongation percentage are 13~17% (national standards), tensile strength about 230-250MPa.And present invention gained silver-based electric contact
Material elongation percentage be up to 29%, resistivity can as little as 1.86 μ Ω cm, tensile strength reach 290MPa, performance difference is very notable.
Finally, it is also necessary to it is noted that listed above is only specific embodiment of the invention.Obviously, the present invention not
It is limited to above embodiment, there can also be many deformations.One of ordinary skill in the art can be straight from present disclosure
Export or all deformations associated are connect, are considered as protection scope of the present invention.
Claims (9)
1. a kind of highly conductive flexible silver-based composite material, it is characterised in that be following components by being calculated with weight
Composition：Silver powder 75~85%, graphene powder 0.5~12%, nano-nickel collosol 5-14.5%, diboron trioxide powder 1-
2.5%, zirconium dioxide powder 0.5-2%, dispersant 0.5~1%.
2. highly conductive flexible silver-based composite material according to claim 1, it is characterised in that the dispersant is carboxymethyl
Cellulose potassium.
3. highly conductive flexible silver-based composite material according to claim 1, it is characterised in that the particle diameter of the silver powder is
0.5~2um, purity 99.99%.
4. highly conductive flexible silver-based composite material according to claim 1, it is characterised in that the layer of the graphene powder
Number is 1-10 atomic layer, and lamella size is 0.05-50um.
5. highly conductive flexible silver-based composite material according to claim 1, it is characterised in that the nano-nickel collosol, grain
Footpath is 30-100nm, concentration 5-20wt%.
6. highly conductive flexible silver-based composite material according to claim 1, it is characterised in that the diboron trioxide powder
It is pure to analyze.
7. highly conductive flexible silver-based composite material according to claim 1, it is characterised in that the zirconium dioxide powder
Particle diameter is 0.5-1 μm, purity 99%.
8. a kind of preparation method of highly conductive flexible silver-based composite material as claimed in claim 1, it is characterised in that including under
State step：
(1) each component is weighed by the proportionate relationship of the composition of raw materials；
(2) nano-nickel collosol is placed in stirring ball-milling equipment, Graphene powder is added while stirring under 1200r/min speed
Body, 40min is sufficiently mixed, obtains compound slurry A；Compound slurry A is placed in ultrasonic device and is ultrasonically treated 1-2h, it is standby；
(3) load weighted diboron trioxide powder, zirconium dioxide powder, the silver powder for accounting for silver powder total amount 20% and deionized water are mixed
Close, add dispersant, the compound slurry B that concentration is 20-30wt% is configured under 2000r/min mixing speed；
(4) compound slurry A and compound slurry B are placed in reactor, 1-2h is reacted under the conditions of 80-160 DEG C, obtain compound material
C is starched, it is standby；
(5) compound slurry C is placed in mechanical stirring equipment, adds remaining silver powder while stirring under 1000r/min speed,
Obtain compound slurry D；
(6) by the spray-dried rear acquisition silver-based composite granules of compound slurry D；
(7) silver-based composite granule is placed in mould, the cold isostatic compaction under 200MPa pressure, obtains silver-based composite material element
Base；
(8) silver-based composite material biscuit is placed in sintering furnace, it is small that 2~4 is sintered under the conditions of air atmosphere, 800~900 DEG C
When, obtain highly conductive flexible silver-based composite material.
9. according to the method for claim 8, it is characterised in that in the step (2), the frequency of ultrasonic device is 50HZ.
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| CN109355523B (en) * | 2018-10-23 | 2020-06-26 | 浙江大学 | Ag/Zn2SnO4Conductive alloy and preparation method thereof |
| CN114101666B (en) * | 2021-09-03 | 2023-08-01 | 叶浩博 | Graphene-based silver-saving electrical contact material and manufacturing method thereof |
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