CN110444318A - A kind of nano-silver thread flexible transparent conducting film with high overlap joint efficiency and excellent resistance to bend(ing) energy - Google Patents
A kind of nano-silver thread flexible transparent conducting film with high overlap joint efficiency and excellent resistance to bend(ing) energy Download PDFInfo
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Abstract
The invention discloses a kind of with the high nano-silver thread flexible transparent conducting film for overlapping efficiency and excellent resistance to bend(ing) energy; the flexible transparent conducting film is to form conductive layer in substrate surface coating nano-silver thread conductive ink first; it is optimized again in conductive layer surface coating together optimization liquid, finally conductive layer surface coating UV protection liquid again after optimization forms UV protective layer.The nano-silver thread surface PVP of flexible transparent conducting film of the present invention is removed, and welding is realized at nano-silver thread network node, so it is low to prepare the conductive film nano-silver thread dosage, conductive film excellent in optical properties obtained, sheet resistance are low, resist bending is had excellent performance, and are suitable for large scale and show and Flexible Displays.
Description
Technical field
The present invention relates to field of electronic display, in particular to it is a kind of with high overlap joint efficiency and excellent resistance to bend(ing) can receive
Rice silver wire flexible transparent conducting film, the conductive film have the characteristics that excellent in optical properties, sheet resistance be low, resist bending is had excellent performance, spy
Not Shi Yongyu large scale show and Flexible Displays.
Background technique
As electronical display industry develops to large scale, the transparent conductive film demand with satisfactory electrical conductivity and high transparency
Amount is continuously increased；Simultaneously because the development of Flexible Displays, proposes requirements at the higher level to the flexibility of transparent conductive film.Existing market is used
Maximum ITO (tin indium oxide) transparent conductive film is measured, high, flexibility difference problem, is not suitable for large scale and shows with sheet resistance
And Flexible Displays.Nano-silver thread in new material is due to superior comprehensive with good in optical property, flexibility and lower sheet resistance etc.
Performance is closed, the optimal alternative materials of ITO are become.
Contact resistance size in nano-silver thread flexible transparent conducting film at nano-silver thread network node, which determines, finally to be led
The electric conductivity of electrolemma, therefore researcher also has conducted extensive research contact resistance at reduction nano-silver thread network node,
It is wherein mainly handled using the methods of thermal weld, photocoagulation, chemistry welding, but these methods all exist centainly at present
Problem, such as: thermal weld needs high-temperature process, is not suitable for the non-refractories flexible parent metal such as PET；The device is complicated for photocoagulation, welding
Window is low, is not suitable for roll-to-roll operation；Chemistry welding is since there are PVP on silver wire surface, so effect is limited.On the other hand,
Due to it is currently used in the market can be mass nano-silver thread substantially from alcohol reduction method be made, need to add stabilizer and
Structure directing agent PVP, although having carried out cleaning treatment after silver wire synthesis, in view of nano-silver thread is molten after cleaning cost and cleaning
A large amount of PVP are still contained on the storage stability problem of liquid, final nano-silver thread surface, to make conductive film obtained in nano-silver thread
Contact resistance increases at network node, and conductive film electrical property is deteriorated.It is simultaneously single physics at nano-silver thread network node
Contact, compactness is poor, and resistance to bend(ing) can need further to improve.
Therefore, nano-silver thread flexible transparent conducting film there are aiming at the problem that, be badly in need of that develop a kind of optical property excellent at present
It is different, sheet resistance is low, resist bending is had excellent performance, shows suitable for large scale and the flexible transparent conducting film of Flexible Displays.
Summary of the invention
In order to avoid above-mentioned prior art shortcoming, the present invention is intended to provide a kind of with high overlap joint efficiency and excellent resistance to
The nano-silver thread flexible transparent conducting film of bending property, to make it have, excellent in optical properties, sheet resistance be low, resistance to bend(ing)
The excellent feature of energy.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of nano-silver thread flexible transparent conducting film with high overlap joint efficiency and excellent resistance to bend(ing) energy, feature exist
In: the nano-silver thread flexible transparent conducting film is to form conductive layer in substrate surface coating nano-silver thread conductive ink first,
It is optimized again in conductive layer surface coating together optimization liquid, finally conductive layer surface coating UV protection again after optimization
Liquid forms UV protective layer.It (is led first in substrate surface coating nano-silver thread compared with existing nano-silver thread flexible transparent conducting film
Electric ink forms conductive layer, then forms UV protective layer in conductive layer surface coating UV protection liquid), difference is to increase together
Optimize the coating of liquid.Further, substantially also there is provided a kind of raising nano-silver thread flexible transparent conducting films to take by the present invention
The method for connecing efficiency and resistance to bend(ing) energy.
Further, the optimization liquid includes following component in parts by mass:
0.5-2 parts of nucleopilic reagent；
0.5-2 parts of reducing agent；
98-99.5 parts of solvent.
Further, the nucleopilic reagent be Grignard Reagent RMgX, azanol, phenylhydrazine, 2,4-dinitrophenylhydrazine, semicarbazides or
Ph3P=CHR；The reducing agent is ethylene glycol, isopropanol or anhydrous citric acid；The solvent is ethyl alcohol, isobutanol and acetic acid second
The ester mixture of 1:1:1 in mass ratio.Further, in the Grignard Reagent RMgX, R be methyl, ethyl, isopropyl,
Cyclopropyl, cyclopenta or allyl, X are chlorine or bromine.
Further, being added in the nano-silver thread conductive ink has the silver salt for accounting for nano-silver thread quality 0.01-2%.
Further, the silver salt is silver acetate, silver fluoride, silver chlorate, silver trifluoroacetate or silver nitrate.
The present invention also provides the preparation methods of the nano-silver thread flexible transparent conducting film, include the following steps:
A, in nano-silver thread conductive ink be added silver salt and stir it is uniform, then flexible parent metal surface coating film forming simultaneously
Drying forms conductive layer；
B, nucleopilic reagent, reducing agent and solvent are sequentially added into dispersion cylinder, mechanical stirring dispersion is uniform, and optimization liquid is made；
Then the conductive layer surface is coated on by the optimization liquid is uniform, heating, drying, the conductive layer after forming optimization；
C, the conductive layer surface coating UV protection liquid after the optimization forms UV protective layer, and it is resistance to further increase conductive film
Hou Xing obtains the nano-silver thread flexible transparent conducting film with high overlap joint efficiency and excellent resistance to bend(ing) energy.
Further, the temperature of heating, drying described in step B be 120-150 DEG C, drying time 1-10min.
Further, nano-silver thread conductive ink of the present invention can be any formula, and silver salt is added wherein, tie
The use for optimizing liquid is closed, can further improve its performance.
Further, the preparation process of above-mentioned conductive layer and UV protective layer uses existing common process, in step A
Coating process can be dimple coating, slot coated, roller coating, spraying or spin coating proceeding.
The present invention is improving nano-silver thread overlap joint efficiency and resist bending in such a way that conductive layer surface is coated with optimization liquid
Performance, principle are: containing nucleopilic reagent in optimization liquid first, the parent therein after optimization liquid is coated on conductive layer surface
Core reagent can penetrate into nano-silver thread surface, carry out addition reaction with the carbonyl of PVP, PVP is detached from nano-silver thread surface, to make
Become silver-colored directly contact containing PVP between nano-silver thread contact point at nano-silver thread network node, so that contact resistance reduces.
Secondly contain silver salt in nano-silver thread conductive layer ink, silver ion can be adsorbed onto and receive under capillary effect when conductive ink is coated with
Rice silver wire node at, optimization liquid heated after application drying course in, using optimization liquid in reducing agent by silver ion reduction at
Silver-colored simple substance is fixed at nano-silver thread node, to welding effect is played at nano-silver thread node, to make at nano-silver thread node
Become face contact from point contact, further decreases contact resistance；And due to having carried out certain welding at node, make its bending resistance
Qu Xingneng is significantly improved.
Compared with prior art, the invention has the following advantages:
The present invention eliminates nano-silver thread surface PVP, makes by being coated with optimization liquid in nano-silver thread layer at transparent layer
Its contact resistance reduces, and overlap joint efficiency improves；And welding is restored at node by silver ion, further increases overlap joint effect
Rate, while improving conductive film resistance to bend(ing) energy.Institute is with the inventive method compared with improving front method: being made with sheet resistance conduction
Film, the nano-silver thread content needed is lower, and it is more preferable that conductive film optical property is made；Under identical silver wire content, it can be made more
Low square resistance conductive film；Simultaneously because its welding effect, keeps conductive film resistance to bend(ing) obtained more preferable, it is aobvious to be more suitable for large scale
Show and Flexible Displays.
Specific embodiment
It elaborates below with reference to embodiment to the present invention, following embodiments are under the premise of the technical scheme of the present invention
Implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following realities
Apply example.
UV protection formula of liquid used in following comparative's example and embodiment is as follows:
Specific preparation method: by UV resin CN9010NS, photoinitiator 1173, levelling agent BYK-333, solvent (butanone: second
Acetoacetic ester and ethylene glycol 1:1:1 in mass ratio are compounded) dispersion cylinder is sequentially added, tetrafluoroethene stirring rod is then used, with
The speed of 500r/min at the uniform velocity stirs 60min, and UV is made and protects liquid.
Comparative example 1
The formula of conductive ink used in this comparative example is as follows:
Nano-silver thread (WJAG1) 0.13%
Disperse coalescing agent (hydroxyethyl cellulose) 0.2%
Deionized water 0ppm 99.67%
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose sequentially add dispersion cylinder, and 30min stirred with 500r/min speed, be made
Conductive ink.
Electrically conducting transparent film preparation: by conductive ink by dimple coating process, being coated on substrate surface, then uses tunnel
100 DEG C of furnace, 2min drying, are made transparent conductive film.
Comparative example 2
The formula of conductive ink used in this comparative example is as follows:
Nano-silver thread (WJAG1) 0.13%
Disperse coalescing agent (hydroxyethyl cellulose) 0.2%
Deionized water 0ppm 99.67%
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose sequentially add dispersion cylinder, and 30min stirred with 500r/min speed, be made
Conductive ink.
Electrically conducting transparent film preparation:
A, conductive ink is coated on substrate surface by dimple coating process, then uses 100 DEG C of continuous tunnel furnace, 2min
Conductive layer is made in drying；
B, UV type protection liquid is passed through into dimple coating process coating in above-mentioned conductive layer surface, then UV solidifies (500mJ/
cm2, 10s) and protective layer is formed, transparent conductive film is made.
Comparative example 3
This comparative example nano-silver thread transparent conductive film conductive ink is formulated as follows:
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose, silver fluoride sequentially add dispersion cylinder, and with the stirring of 500r/min speed
Conductive ink is made in 30min.
Electrically conducting transparent film preparation:
A, conductive ink is coated on substrate surface by dimple coating process, then uses 100 DEG C of continuous tunnel furnace, 2min
Conductive layer is made in drying；
B, above-mentioned UV type protection liquid is passed through into dimple coating process coating in above-mentioned conductive layer surface, then UV solidifies
(500mJ/cm2, 10s) and protective layer is formed, transparent conductive film is made.
Embodiment 1
The present embodiment nano-silver thread transparent conductive film conductive ink is formulated as follows:
Nano-silver thread (WJAG1) 0.13%
Disperse coalescing agent (hydroxyethyl cellulose) 0.2%
Deionized water 0ppm 99.67%
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose sequentially add dispersion cylinder, and 30min stirred with 500r/min speed, be made
Conductive ink.
The present embodiment nano-silver thread transparent conductive film is as follows with optimization formula of liquid:
1 part of methyl-magnesium-bromide
1 part of ethylene glycol
98 parts of solvent (ethyl alcohol, isobutanol, ethyl acetate mass ratio 1:1:1)
Specific preparation method: methyl-magnesium-bromide, ethylene glycol, solvent are sequentially added into dispersion cylinder, and with 500r/min speed
30min is stirred, optimization liquid is made.
Electrically conducting transparent film preparation:
A, conductive ink is coated on substrate surface by dimple coating process, then uses 100 DEG C of continuous tunnel furnace, 2min
Conductive layer is made in drying；
B, will optimize liquid by dimple coating process coating (a) conductive layer surface, then using 140 DEG C of continuous tunnel furnace,
5min drying, the conductive layer after optimization is made；
C, above-mentioned UV type protection liquid is passed through into conductive layer surface of the dimple coating process coating after above-mentioned optimization, then UV
Solidify (500mJ/cm2, 10s) and protective layer is formed, transparent conductive film is made.
Embodiment 2
The present embodiment nano-silver thread transparent conductive film conductive ink is formulated as follows:
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose, silver fluoride sequentially add dispersion cylinder, and with the stirring of 500r/min speed
Conductive ink is made in 30min.
The present embodiment nano-silver thread transparent conductive film is as follows with optimization formula of liquid:
1 part of methyl-magnesium-bromide
1 part of ethylene glycol
98 parts of solvent (ethyl alcohol, isobutanol, ethyl acetate mass ratio 1:1:1)
Specific preparation method: methyl-magnesium-bromide, ethylene glycol, solvent are sequentially added into dispersion cylinder, and with 500r/min speed
30min is stirred, optimization liquid is made.
Electrically conducting transparent film preparation:
A, conductive ink is coated on substrate surface by dimple coating process, then uses 100 DEG C of continuous tunnel furnace, 2min
Conductive layer is made in drying；
B, will optimize liquid by dimple coating process coating (a) conductive layer surface, then using 140 DEG C of continuous tunnel furnace,
5min drying, the conductive layer after optimization is made；
C, above-mentioned UV type protection liquid is passed through into conductive layer surface of the dimple coating process coating after above-mentioned optimization, then UV
Solidify (500mJ/cm2, 10s) and protective layer is formed, transparent conductive film is made.
Embodiment 3
The present embodiment nano-silver thread transparent conductive film conductive ink is formulated as follows:
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose, silver nitrate sequentially add dispersion cylinder, and with the stirring of 500r/min speed
Conductive ink is made in 30min.
The present embodiment nano-silver thread transparent conductive film is as follows with optimization formula of liquid:
1 part of methyl-magnesium-bromide
1 part of ethylene glycol
98 parts of solvent (ethyl alcohol, isobutanol, ethyl acetate mass ratio 1:1:1)
Specific preparation method: methyl-magnesium-bromide, ethylene glycol, solvent are sequentially added into dispersion cylinder, and with 500r/min speed
30min is stirred, optimization liquid is made.
Electrically conducting transparent film preparation:
A, conductive ink is coated on substrate surface by dimple coating process, then uses 100 DEG C of continuous tunnel furnace, 2min
Conductive layer is made in drying；
B, will optimize liquid by dimple coating process coating (a) conductive layer surface, then using 140 DEG C of continuous tunnel furnace,
5min drying, the conductive layer after optimization is made；
C, above-mentioned UV type protection liquid is passed through into conductive layer surface of the dimple coating process coating after above-mentioned optimization, then UV
Solidify (500mJ/cm2, 10s) and protective layer is formed, transparent conductive film is made.
Embodiment 4
The present embodiment nano-silver thread transparent conductive film conductive ink is formulated as follows:
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose, silver nitrate sequentially add dispersion cylinder, and with the stirring of 500r/min speed
Conductive ink is made in 30min.
The present embodiment nano-silver thread transparent conductive film is as follows with optimization formula of liquid:
1 part of allylmgcl
1 part of ethylene glycol
98 parts of solvent (ethyl alcohol, isobutanol, ethyl acetate mass ratio 1:1:1)
Specific preparation method: allylmgcl, ethylene glycol, solvent are sequentially added into dispersion cylinder, and with 500r/min speed
Degree stirring 30min, is made optimization liquid.
Electrically conducting transparent film preparation:
A, conductive ink is coated on substrate surface by dimple coating process, then uses 100 DEG C of continuous tunnel furnace, 2min
Conductive layer is made in drying；
B, will optimize liquid by dimple coating process coating (a) conductive layer surface, then using 140 DEG C of continuous tunnel furnace,
5min drying, the conductive layer after optimization is made；
C, above-mentioned UV type protection liquid is passed through into conductive layer surface of the dimple coating process coating after above-mentioned optimization, then UV
Solidify (500mJ/cm2, 10s) and protective layer is formed, transparent conductive film is made.
Embodiment 5
The present embodiment nano-silver thread transparent conductive film conductive ink is formulated as follows:
Specific preparation method: by deionized water, nano-silver thread WJAG1, (line footpath 20nm, draw ratio 1000-2000, Hefei are micro-
Brilliant material Science and Technology Ltd.), hydroxyethyl cellulose, silver nitrate sequentially add dispersion cylinder, and with the stirring of 500r/min speed
Conductive ink is made in 30min.
The present embodiment nano-silver thread transparent conductive film is as follows with optimization formula of liquid:
1 part of allylmgcl
1 part of anhydrous citric acid
98 parts of solvent (ethyl alcohol, isobutanol, ethyl acetate mass ratio 1:1:1)
Specific preparation method: allylmgcl, anhydrous citric acid, solvent are sequentially added into dispersion cylinder, and with 500r/
Min speed stirs 30min, and optimization liquid is made.
Electrically conducting transparent film preparation:
A, conductive ink is coated on substrate surface by dimple coating process, then uses 100 DEG C of continuous tunnel furnace, 2min
Conductive layer is made in drying；
B, liquid will be optimized by dimple coating process coating in the conductive layer surface of (a), then use 140 DEG C of continuous tunnel furnace,
5min drying, the conductive layer after optimization is made；
C, above-mentioned UV type protection liquid is passed through into conductive layer surface of the dimple coating process coating after above-mentioned optimization, then UV
Solidify (500mJ/cm2, 10s) and protective layer is formed, transparent conductive film is made.
Table 1: comparative example 1-3 performance test
As comparative example 1-3 comparison result it is found that conductive film weatherability made from single conductive layer and resistance to bend(ing) can very
Difference；It is formed on its surface after UV protective layer, weatherability is up to standard, and resistance to bend(ing) can be obviously improved；And individually in the conductive layer
It adds silver salt (silver fluoride), is not coated with optimization liquid, conductive film properties are not improved.
Table 2: comparative example 3 and embodiment 1-2 performance test
By the comparison result of comparative example 3 and embodiment 1 it is found that not made an amendment to conductive ink, only in conductive layer surface
Coating optimization liquid, can effectively improve the overlap joint efficiency of conductive film, and conductive film sheet resistance reduces obvious, and as a result illustrating to optimize liquid can be with
Effectively remove nano-silver thread surface PVP；By the comparison result of embodiment 1 and embodiment 2 it is found that adding silver salt in conductive ink
(silver fluoride), and be coated with optimization liquid in conductive layer surface, can further decrease conductive film sheet resistance, and its resistance to bend(ing) can and
Improved weathering is obvious, illustrates that the reducing agent optimized in liquid plays very well the silver fluoride inside conductive layer at network node
Reduction, realize welding.
Table 3: embodiment 2-5 performance test
By the comparison result of embodiment 2-5 it is found that adding different silver salt in conductive ink, optimization liquid is tried using different nucleophilics
Agent and reducing agent can effectively improve overlap joint efficiency and resistance to bend(ing) energy.
The above is only exemplary embodiment of the present invention, are not intended to limit the invention, all in spirit of the invention
With any modifications, equivalent replacements, and improvements made within principle etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of nano-silver thread flexible transparent conducting film with high overlap joint efficiency and excellent resistance to bend(ing) energy, it is characterised in that:
The nano-silver thread flexible transparent conducting film be first substrate surface coating nano-silver thread conductive ink formed conductive layer, then
Optimization liquid optimizes together for the conductive layer surface coating, and finally conductive layer surface coating UV again after optimization protects liquid shape
At UV protective layer.
2. nano-silver thread flexible transparent conducting film according to claim 1, which is characterized in that the optimization liquid includes pressing matter
Measure the following component of part meter:
0.5-2 parts of nucleopilic reagent；
0.5-2 parts of reducing agent；
98-99.5 parts of solvent.
3. nano-silver thread flexible transparent conducting film according to claim 2, it is characterised in that: the nucleopilic reagent is grignard
Reagent RMgX, azanol, phenylhydrazine, 2,4 dinitrophenyl hydrazine, semicarbazides or Ph3P=CHR；The reducing agent is ethylene glycol, isopropanol
Or anhydrous citric acid.
4. nano-silver thread flexible transparent conducting film according to claim 2 or 3, it is characterised in that: the solvent be ethyl alcohol,
Isobutanol and the ethyl acetate mixture of 1:1:1 in mass ratio.
5. nano-silver thread flexible transparent conducting film according to claim 3, it is characterised in that: in the Grignard Reagent RMgX
In, R is methyl, ethyl, isopropyl, cyclopropyl, cyclopenta or allyl, and X is chlorine or bromine.
6. nano-silver thread flexible transparent conducting film according to claim 1 or 2, it is characterised in that: in the nano-silver thread
Being added in conductive ink has the silver salt for accounting for nano-silver thread quality 0.01-2%.
7. nano-silver thread flexible transparent conducting film according to claim 6, it is characterised in that: the silver salt be silver acetate,
Silver fluoride, silver chlorate, silver trifluoroacetate or silver nitrate.
8. the preparation method of nano-silver thread flexible transparent conducting film, feature described in a kind of any one of claim 1~7 exist
In including the following steps:
A, silver salt is added in nano-silver thread conductive ink and stirs uniform, then in flexible parent metal surface coating film forming and dries
It is dry, form conductive layer；
B, nucleopilic reagent, reducing agent and solvent are sequentially added into dispersion cylinder, mechanical stirring dispersion is uniform, and optimization liquid is made；
Then the conductive layer surface is coated on by the optimization liquid is uniform, heating, drying, the conductive layer after forming optimization；
C, the conductive layer surface coating UV protection liquid after the optimization forms UV protective layer, and it is weather-proof to further increase conductive film
Property, obtain the nano-silver thread flexible transparent conducting film with high overlap joint efficiency and excellent resistance to bend(ing) energy.
9. preparation method according to claim 8, it is characterised in that: the temperature of heating, drying described in step B is 120-150
DEG C, drying time 1-10min.
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| CN112562887A (en) * | 2020-11-18 | 2021-03-26 | 深圳市华科创智技术有限公司 | Nano silver wire transparent conductive film with excellent bending resistance |
| CN113571257A (en) * | 2021-07-22 | 2021-10-29 | 苏州诺菲纳米科技有限公司 | Method for improving lap joint of silver paste and nano silver wire conductive film |
| CN113878127A (en) * | 2021-09-15 | 2022-01-04 | 昆明贵研新材料科技有限公司 | Method for auxiliary synthesis of superfine nano-silver wire by taking Grignard reagent as auxiliary agent |
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| CN108766666A (en) * | 2018-06-07 | 2018-11-06 | 乐凯华光印刷科技有限公司 | A kind of low resistance, nano-silver thread transparent conductive film of high transparency and preparation method thereof |
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| CN112562887B (en) * | 2020-11-18 | 2022-07-15 | 深圳市华科创智技术有限公司 | Nano silver wire transparent conductive film with excellent bending resistance |
| CN113571257A (en) * | 2021-07-22 | 2021-10-29 | 苏州诺菲纳米科技有限公司 | Method for improving lap joint of silver paste and nano silver wire conductive film |
| CN113878127A (en) * | 2021-09-15 | 2022-01-04 | 昆明贵研新材料科技有限公司 | Method for auxiliary synthesis of superfine nano-silver wire by taking Grignard reagent as auxiliary agent |
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