CN105714397A - Preparation method of nano cuprous sulfide/polyvinyl alcohol composite conductive fiber - Google Patents
Preparation method of nano cuprous sulfide/polyvinyl alcohol composite conductive fiber Download PDFInfo
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- CN105714397A CN105714397A CN201610209815.XA CN201610209815A CN105714397A CN 105714397 A CN105714397 A CN 105714397A CN 201610209815 A CN201610209815 A CN 201610209815A CN 105714397 A CN105714397 A CN 105714397A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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Abstract
The invention belongs to the field of preparation of composite conductive fibers and relates to a preparation method of a polyvinyl alcohol composite conductive fiber. According to the preparation method, firstly, polyvinyl alcohol is used as a base body, copper sulfate and sodium thiosulfate are used as raw materials, nano cuprous sulfide is produced in situ through a chemical reaction in a polyvinyl alcohol aqueous solution, a nano cuprous sulfide/polyvinyl alcohol composite spinning solution is obtained, and the nano cuprous sulfide/polyvinyl alcohol composite conductive fiber with lasting conductivity is prepared from the spinning solution in a wet spinning manner. The traditional polyvinyl alcohol wet spinning technology is adopted, existing requirement is not required to be transformed or replaced, the equipment investment is low, the technological route is simple, the operability is high, and the production efficiency is high. According to the preparation technology of the conductive fiber, the conductive network is formed in the fiber, a conductive layer cannot fall off during usage, the effect of the use environment is avoided, and the conductive function is lasting.
Description
Technical field
The invention belongs to composite conducting fiber preparation field, the preparation method relating to a kind of polyvinyl alcohol composite conducting fiber.
Background technology
In recent years, along with developing rapidly and universal of computer, telecommunications, microwave oven etc., electromagnetic radiation in human lives's working environment is day by day serious thus the normal operation of electronic equipment and the physiological health of the mankind are brought a lot of negative effect by that produce Electromagnetic Interference, for preventing static interference and Electromagnetic Interference, from mid-term in 20th century so far, for various uses, develop the material of various antistatic and electromagnetic shielding.Recent decades, the emphasis of research has turned to conductive fiber more, the antistatic effect of conductive fiber is significantly lasting, and not by the impact of ambient humidity, conductive layer reaches certain thickness or after conductive component reaches certain proportion, there is excellent electro-magnetic screen function, therefore conductive fiber development and application increasingly come into one's own.
The preparation method of conductive fiber has many kinds, and along with deepening continuously of research, according to the final performance of prepared fiber and preparation technology, people have been phased out some preparation methoies fallen behind.At present, the method being prepared into antistatic fibre mainly has three kinds: one to be with either physically or chemically making fiber surface form the coat of metal at textile surfaces such as fibers, this method often makes the feel of fiber become thick and stiff due to the coat of metal formed, it is difficult to textile process, and investment of production equipment is big, efficiency is low, and production cost is high；Two is chemically form semiconductor lamella at fiber surface, and chemical method technique is relatively simple, affects little on the physical and mechanical properties of fiber, and electric conductivity is better, but conduction durability is poor；Three is that electrically conductive particles is mixed in spinning melt; made the conductive fiber of skin-core structure or island structure by composite spinning, the Conductivity of Fiber electrical endurance prepared in this way is excellent, and less because adding conducting particles; do not damage the physical property of fiber, thus receive significant attention.But, when adopting this technique to prepare antistatic fibre, commonly used conducting particles size mostly is a μm level, does not have the characteristic of nano material, and in molding process, often increases the weight of the loss of equipment, is unfavorable for reducing production cost.Therefore, development cost conductive fiber low, function admirable is just particularly important.
Metal sulfide all has special performance in optics, Optical Electro-Chemistry, catalysis, environmental protection etc..They have good chemically and thermally stability, are a kind of good photoelectric materials.The characteristic utilizing metal sulfide is preferably at most fiber surface chemical reaction method to the method producing conductive fiber in application at present, this method is mainly through chemical treatment, namely by the dipping of reactant liquor, produce absorption at fiber surface, then pass through chemical reaction and make metal sulfide cover fiber surface.The method advantage is in that technique is simple, less costly, and the intensity of fiber, flexibility, slipping equivalent damage is less.In the eighties in 20th century, Japan is just developed into this kind of conductive fiber.Conductive compositions and electrical conduction mechanism have also been studied by specially, and the surface such as Japan's development covers the conductive acrylic fibre of the sulfide of copper, is first processed in copper ions solution by acrylon, then processes in reducing agent, the Cu on fiber2+Become Cu+With-CN complexation, the further conductive material of the sulfide of formation copper.Owing to these conductive materials define network on fibre structure, therefore electric conductivity is fine.Domestic patent 87104625.3,201510188325.1,200810084225.4 etc. all adopts production conductive fiber in this way.But, this Conductive PAN Fibre conduction persistency not good, the effect of the moisture content in nature, the oxygen in air and weak acid or weak base, it is possible to make the copper sulfide of conduction come off so that fiber loses electric conductivity.
If will conduct electricity in the nano particle ordered fibre-forming polymer substrate being scattered in routine of cuprous sulfide, then can both advantage comprehensive better, obtain high performance composite conducting fiber.But Conventional processing methods prepared by polymer base inorganic filler composite materials such as double; two rollers open refining, Screw Extrusion, melting mixing, solution mixing etc. in the ordinary course of things can not for preparing polymer base inorganic nano-composite material because these conventional methods are inherently disperseed and the yardstick that mixes is more than hundreds of nanometer.Inorganic nanoparticles can owing to having high surface, there is very strong agglomeration tendency, acting on heat power in the course of processing of polymer mixed etc., destroying it was scattered poised state originally, what frequently result in is that nanoparticle agglomerates becomes hundreds of nanometer even composite of micro-meter scale, thus losing peculiar function and the effect of nano-particle.
Summary of the invention
For solving the technical barrier that nano material and conventional fibre cannot be merged by conventional machining, the preparation method that the present invention provides a kind of nanometer of cuprous sulfide/polyvinyl alcohol composite conducting fiber.
The present invention by the following technical solutions, specifically comprises the following steps that
A kind of preparation method of nanometer of cuprous sulfide/polyvinyl alcohol composite conducting fiber, the step of the described nanometer cuprous sulfide/polyvinyl alcohol composite conducting fiber of preparation is as follows:
(1) copper sulfate is dissolved in water, forms copper sulfate solution, polyvinyl alcohol is added in copper sulfate solution, be warmed up to 50 DEG C～97 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 1～3, prepare a solution；
(2) being dissolved in water by sodium thiosulfate, form sodium thiosulfate solution, polyvinyl alcohol adds in sodium thiosulfate solution, is warmed up to 50 DEG C～97 DEG C and makes polyvinyl alcohol dissolve, and prepares b solution；
(3) a solution and b solution are mixed, react 10～60 minutes at 75 DEG C～90 DEG C, obtain cuprous sulfide/polyvinyl alcohol spin dope；
(4) spinning head of 0.08～0.1mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 40 DEG C～80 DEG C, spraying from spinning head, dynamic analysis of spinning is coagulation forming in coagulating bath, fiber, through 4～10 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.
In described step (1), the kind of polyvinyl alcohol is 1788 or 1799, and the mass concentration of copper sulfate is 1.5%～7.5%, and the mass concentration of polyvinyl alcohol is 8%～16%.
In described step (2), the mass concentration of polyvinyl alcohol is 8%～16%, and the mass concentration of sodium thiosulfate solution is 1.5%～7.5%.
In described step (3), a solution is 1:1～1:3 with the mass ratio of b solution.
In described step (4), coagulating bath is the aqueous sodium persulfate solution of 38%～42%, and the temperature of coagulation forming is 35 DEG C～55 DEG C.
The beneficial effects of the present invention is:
(1) present invention is first with polyvinyl alcohol for matrix, with copper sulfate, sodium thiosulfate for raw material, makes cuprous learning of nanometer sulfuration react in-situ preparation in polyvinyl alcohol water solution.This method makes nanometer cuprous sulfide granule by chemical reaction in-situ preparation under the controlled environment that polyvinyl alcohol provides, thus realizing the preparation of PVA-based nanometer of cuprous sulfide composite conducting fiber.Polyvinyl alcohol on molecular structure with highly polar group hydroxy, this intensity level group can and the copper ion of cuprous sulfide between form the interaction that ionic bond, complex coordination key etc. are strong, thus the mutual collision probability reduced between microgranule.Polymer chain can stop the excessive gathering of granule simultaneously, so make cuprous sulfide nano-particle dispersed in polyvinyl alcohol matrix, in the less situation of conducting particles content, just can form conductive path, make fiber have good electric conductivity and physical and mechanical properties.
(2) what the present invention adopted is traditional Wet PVA spinning technique, the elimination of chemical reaction by-product can be realized while spinning solution solidification in aqueous sodium persulfate solution, without existing equipment being transformed or changing, equipment investment is few, process route is simple, workable, production efficiency is high.
(3) technology of conductive fiber prepared by the present invention makes conductive network being internally formed at fiber, will not produce coming off of conductive layer in the process used, and also not by the impact using environment, conducting function has persistency.
Detailed description of the invention
Embodiment 1
(1) 15 grams of copper sulfate are dissolved in 905 grams of water and form copper-bath, it is subsequently adding 80 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) to be warmed up to 50 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 1, obtain a solution.
(2) 15 grams of sodium thiosulfate are dissolved in 905 grams of water formation hypo solution, are subsequently adding 80 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) and are warmed up to 50 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 500 grams of a solution and 500 grams of b solution mixing, it is warming up to 75 DEG C and reacts 10 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.08mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 40 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 35 DEG C, concentration be 38% aqueous sodium persulfate solution in coagulation forming, fiber, through 4 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 10-6S/cm, intensity is 3.26cN/dtex.
Embodiment 2
(1) 30 grams of copper sulfate are dissolved in 890 grams of water and form copper-bath, it is subsequently adding 80 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) to be warmed up to 92 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 2, prepare a solution.
(2) 15 grams of sodium thiosulfate are dissolved in 905 grams of water formation hypo solution, are subsequently adding 80 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) and are warmed up to 95 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 400 grams of a solution and 800 grams of b solution mixing, it is warming up to 85 DEG C and reacts 20 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.08mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 50 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 50 DEG C, concentration be 42% aqueous sodium persulfate solution in coagulation forming, fiber, through 4 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 10-5S/cm, intensity is 2.91cN/dtex.
Embodiment 3
(1) 45 grams of copper sulfate are dissolved in 790 grams of water and form copper-bath, it is subsequently adding 160 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1788) to be warmed up to 50 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 2, prepare a solution.
(2) 15 grams of sodium thiosulfate are dissolved in 905 grams of water formation hypo solution, are subsequently adding 160 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1788) and are warmed up to 55 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 300 grams of a solution and 900 grams of b solution mixing, it is warming up to 75 DEG C and reacts 60 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.1mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 80 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 55 DEG C, concentration be 38% aqueous sodium persulfate solution in coagulation forming, fiber, through 10 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 10-4S/cm, intensity is 3.81cN/dtex.
Embodiment 4
(1) 75 grams of copper sulfate are dissolved in 780 grams of water and form copper-bath, it is subsequently adding 145 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1788) to be warmed up to 50 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 3, prepare a solution.
(2) 75 grams of sodium thiosulfate are dissolved in 780 grams of water formation hypo solution, are subsequently adding 145 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1788) and are warmed up to 65 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 500 grams of a solution and 500 grams of b solution mixing, it is warming up to 75 DEG C and reacts 30 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.1mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 75 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 55 DEG C, concentration be 38% aqueous sodium persulfate solution in coagulation forming, fiber, through 8 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 10-3S/cm, intensity is 3.33cN/dtex.
Embodiment 5
(1) 60 grams of copper sulfate are dissolved in 780 grams of water and form copper-bath, it is subsequently adding 160 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) to be warmed up to 97 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 1, prepare a solution.
(2) 30 grams of sodium thiosulfate are dissolved in 850 grams of water formation hypo solution, are subsequently adding 120 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) and are warmed up to 95 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 300 grams of a solution and 600 grams of b solution mixing, it is warming up to 80 DEG C and reacts 10 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.08mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 70 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 35 DEG C, concentration be 40% aqueous sodium persulfate solution in coagulation forming, fiber, through 7 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 10-5S/cm, intensity is 3.02cN/dtex.
Embodiment 6
(1) 60 grams of copper sulfate are dissolved in 780 grams of water and form copper-bath, it is subsequently adding 140 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1788) to be warmed up to 70 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 2, prepare a solution.
(2) 45 grams of sodium thiosulfate are dissolved in 805 grams of water formation hypo solution, are subsequently adding 150 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1788) and are warmed up to 50 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 500 grams of a solution and 750 grams of b solution mixing, it is warming up to 80 DEG C and reacts 40 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.1mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 85 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 47 DEG C, concentration be 39% aqueous sodium persulfate solution in coagulation forming, fiber, through 7 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 10-3S/cm, intensity is 2.78cN/dtex.
Embodiment 7
(1) 60 grams of copper sulfate are dissolved in 780 grams of water and form copper-bath, it is subsequently adding 160 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) to be warmed up to 97 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 1, prepare a solution.
(2) 30 grams of sodium thiosulfate are dissolved in 850 grams of water formation hypo solution, are subsequently adding 120 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) and are warmed up to 95 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 300 grams of a solution and 600 grams of b solution mixing, it is warming up to 80 DEG C and reacts 10 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.08mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 70 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 35 DEG C, concentration be 40% aqueous sodium persulfate solution in coagulation forming, fiber, through 7 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 10-5S/cm, intensity is 3.35cN/dtex.
Embodiment 8
(1) 75 grams of copper sulfate are dissolved in 765 grams of water formation copper-bath, are subsequently adding 160 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) and are warmed up to 97 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid, adjustment pH to 3 after forming clear solution, obtain a solution.
(2) 75 grams of sodium thiosulfate are dissolved in 765 grams of water formation hypo solution, are subsequently adding 160 grams of polyvinyl alcohol (kind of polyvinyl alcohol is 1799) and are warmed up to 97 DEG C and make polyvinyl alcohol dissolve, obtain b solution.
(3) by 500 grams of a solution and 1500 grams of b solution mixing, it is warming up to 90 DEG C and reacts 60 minutes, obtain cuprous sulfide/polyvinyl alcohol spin dope.
(4) spinning head of 0.1mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 80 DEG C, spray from spinning head, dynamic analysis of spinning temperature be 55 DEG C, concentration be 42% aqueous sodium persulfate solution in coagulation forming, fiber, through 10 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.The electrical conductivity of fiber is 2 × 10-6S/cm, intensity is 3.71cN/dtex.
Claims (5)
1. the preparation method of one kind of nanometer of cuprous sulfide/polyvinyl alcohol composite conducting fiber, it is characterised in that: the step of the described nanometer cuprous sulfide/polyvinyl alcohol composite conducting fiber of preparation is as follows:
(1) copper sulfate is dissolved in water, forms copper sulfate solution, polyvinyl alcohol is added in copper sulfate solution, be warmed up to 50 DEG C～97 DEG C and make polyvinyl alcohol dissolve, add glacial acetic acid after forming clear solution, regulate pH to 1～3, prepare a solution；
(2) being dissolved in water by sodium thiosulfate, form sodium thiosulfate solution, polyvinyl alcohol adds in sodium thiosulfate solution, is warmed up to 50 DEG C～97 DEG C and makes polyvinyl alcohol dissolve, and prepares b solution；
(3) a solution and b solution are mixed, react 10～60 minutes at 75 DEG C～90 DEG C, obtain cuprous sulfide/polyvinyl alcohol spin dope；
(4) spinning head of 0.08～0.1mm is adopted, by spinning solution pressure filtration, deaeration, through dosing pump, filter at 40 DEG C～80 DEG C, spraying from spinning head, dynamic analysis of spinning is coagulation forming in coagulating bath, fiber, through 4～10 times of stretchings, obtains a nanometer cuprous sulfide/polyvinyl alcohol conductive fiber.
2. the preparation method of as claimed in claim 1 nanometer of cuprous sulfide/polyvinyl alcohol composite conducting fiber, it is characterised in that: in described step (1), the kind of polyvinyl alcohol is 1788 or 1799；The mass concentration of copper sulfate is 1.5%～7.5%, and the mass concentration of polyvinyl alcohol is 8%～16%.
3. the preparation method of as claimed in claim 1 nanometer of cuprous sulfide/polyvinyl alcohol composite conducting fiber, it is characterised in that: in described step (2), the mass concentration of polyvinyl alcohol is 8%～16%, and the mass concentration of sodium thiosulfate solution is 1.5%～7.5%.
4. the preparation method of as claimed in claim 1 nanometer of cuprous sulfide/polyvinyl alcohol composite conducting fiber, it is characterised in that: in described step (3), a solution is 1:1～1:3 with the mass ratio of b solution.
5. the preparation method of as claimed in claim 1 nanometer of cuprous sulfide/polyvinyl alcohol composite conducting fiber, it is characterised in that: in described step (4), coagulating bath is the aqueous sodium persulfate solution of 38%～42%, and the temperature of coagulation forming is 35 DEG C～55 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106910875A (en) * | 2017-03-06 | 2017-06-30 | 常州大学 | A kind of CuS/Cu for lithium-sulfur cell2The preparation method of S/S trielement composite materials |
| CN109680352A (en) * | 2018-11-27 | 2019-04-26 | 广州易森防护用品科技有限公司 | A kind of preparation method of the conductive fiber for gloves |
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| CN1657662A (en) * | 2004-02-18 | 2005-08-24 | 可乐丽股份有限公司 | Conductive polyvinyl alcohol fiber |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106910875A (en) * | 2017-03-06 | 2017-06-30 | 常州大学 | A kind of CuS/Cu for lithium-sulfur cell2The preparation method of S/S trielement composite materials |
| CN106910875B (en) * | 2017-03-06 | 2019-10-11 | 常州大学 | A kind of CuS/Cu for lithium-sulfur cell2The preparation method of S/S trielement composite material |
| CN109680352A (en) * | 2018-11-27 | 2019-04-26 | 广州易森防护用品科技有限公司 | A kind of preparation method of the conductive fiber for gloves |
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