CN104108709A - Porous graphene and preparation method thereof - Google Patents
Porous graphene and preparation method thereof Download PDFInfo
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- CN104108709A CN104108709A CN201410361303.6A CN201410361303A CN104108709A CN 104108709 A CN104108709 A CN 104108709A CN 201410361303 A CN201410361303 A CN 201410361303A CN 104108709 A CN104108709 A CN 104108709A
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Abstract
The invention relates to porous graphene and a preparation method thereof. The preparation method comprises the following steps: heating a mixture of an organic acid and salt or organic salt in a non-oxidizing atmosphere to 300-1600 DEG C to obtain a mixture of porous graphene and a metallic oxide; and removing the metallic oxide in the mixture to obtain the porous graphene. The porous graphene is prepared by heating the mixture of an organic acid and salt or organic salt in the non-oxidizing atmosphere by means of the idea of carbonization of organic salt and nucleation of inorganic oxide. The method has the advantages of simple process, short production period, macroscopy and the like. The porous graphene prepared by the method has the characteristics of porosity and big specific surface area and can be applied to the fields of cathodes of lithium ion batteries, electrodes of supercapacitors, optical catalyst carriers, adsorbents and the like.
Description
Technical field
The present invention relates to carbon material technical field, is a kind of porous graphene and preparation method thereof specifically.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the Two-dimensional Carbon material of the monoatomic layer thickness of honeycomb lattice.Obtain after single-layer graphene by mechanically peel legal system first from Geim group in 2004, Graphene, with its unique structure and excellent electric property, thermal property, mechanical property and optical property, attracts wide attention in chemistry, physics and material educational circles.At present, Graphene has huge potential application at aspects such as lithium ion battery, ultracapacitor, lead-acid cell, photochemical catalysis, protective system, solid lubricant, touch-screens.The basis of realizing these application and prepare on a large scale high-quality grapheme material.The preparation method of the Graphene of prior art mainly contains: mechanically peel method, liquid phase stripping method, epitaxial growth method, chemical Vapor deposition process, electrochemical method, arc process, graphite oxide reduction method etc.There is following technical problem in these methods: mechanically peel method, epitaxial growth method, chemical Vapor deposition process, arc process etc. are prepared graphite and be difficult for mass-producing, has the problem that yields poorly; Liquid phase stripping method charge stripping efficiency is low; Although graphite oxide reduction method can be used for preparing in a large number Graphene, it exists the production cycle long, and environmental pollution is large, makes the shortcomings such as the easy reunion of Graphene.Therefore, development simple, fast, preparation method that can macroblock quantization is the focus of Graphene research field.
Porous graphene, because having the hole of nano-scale in its lamella, makes it when as the energy, catalysis or sorbing material, not only has higher specific surface area, also has good mass transfer effect simultaneously, has given full play to the advantage of two-dimensional nano sheet layer material.
Summary of the invention
In order to make up above-mentioned the deficiencies in the prior art, technical problem to be solved by this invention is to provide a kind of porous graphene preparation method quick, large-scale production that realizes.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A kind of porous graphene preparation method, comprising:
The mixture of organic acid and salt or organic salt are heated to 350-1600 DEG C under non-oxidizing atmosphere, obtain the mixture of porous graphene and metal oxide;
Remove the metal oxide in mixture, obtain porous graphene;
Wherein, described organic salt is selected from one or more in alkyl soap and the oleate that Citrate trianion, gluconate, tartrate, D-VB5 salt, threose acid salt, the carbonatoms of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth are 8-24;
Wherein, described organic acid is selected from one or more in alkyl lipid acid and the oleic acid that citric acid, gluconic acid, tartrate, D-VB5, threonic acid, carbonatoms are 8-24;
Wherein, described salt is selected from one or more in acetate, nitrate, chlorate, Bromide and the iodized salt of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth.
Beneficial effect of the present invention is: technique is simple, with short production cycle, be produced on a large scale.The standby Graphene of this legal system has porousness, feature that specific surface area is large, can be applicable to the every field such as lithium ion battery negative, electrode of super capacitor, carrier of photocatalyst, sorbent material.
Brief description of the drawings
Figure 1 shows that porous graphene prepared by the embodiment of the present invention 1 and the scanning electron microscope (SEM) photograph of calcium oxide mixture;
Figure 2 shows that the scanning electron microscope (SEM) photograph of porous graphene prepared by the embodiment of the present invention 1.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, being realized object and effect, below in conjunction with embodiment and coordinate accompanying drawing to be explained in detail.
The design of most critical of the present invention is: by heat the mixture of organic salt or organic acid and salt in non-oxidizing atmosphere, utilize organic salt carbonization and inorganic oxide nucleation theory, prepare porous graphene.The method have technique simple, with short production cycle, can macroblock quantization etc. advantage, the Graphene that the method prepares has porousness, feature that specific surface area is large, can be applicable to the every field such as lithium ion battery negative, electrode of super capacitor, carrier of photocatalyst, sorbent material.
Porous graphene preparation method provided by the invention, comprising:
The mixture of organic acid and salt or organic salt are heated to 350-1600 DEG C under non-oxidizing atmosphere, obtain the mixture of porous graphene and metal oxide;
Remove the metal oxide in mixture, obtain porous graphene;
Wherein, described organic salt is selected from one or more in alkyl soap and the oleate that Citrate trianion, gluconate, tartrate, threose acid salt, the carbonatoms of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth are 8-24;
Wherein, described organic acid is selected from one or more in alkyl lipid acid and the oleic acid that citric acid, gluconic acid, tartrate, threonic acid, carbonatoms are 8-24;
Wherein, described salt is selected from one or more in acetate, nitrate, chlorate, Bromide and the iodized salt of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth.
The mechanism that the present invention prepares porous graphene is as follows:
In the mixed system of rich carbon organic salt or rich carbon organic acid and salt, rich carbon organic acid or rich carbon organic salt as carbon source in high temperature non-oxidizing atmosphere, through pyrolysis, the metal oxide surface that carbon atom is grown in position becomes nuclear rearrangement, reset the growth that presents two-dimensional directional according to oxide surface template, and continuity is good, thereby obtain the mixture of porous graphene and metal oxide.Metal oxide has the sour feature that is dissolved in, and therefore mixture, after cleanup acid treatment, can obtain pure porous graphene.
From foregoing description, beneficial effect of the present invention is:
Because the present invention only needs the mixture by heat organic salt or organic acid and salt in non-oxidizing atmosphere, can prepare the mixture of porous graphene and metal oxide, the follow-up metal oxide that can remove in mixture by conventional impurity removal process such as pickling obtains the more much higher hole of purity Graphene, therefore compared to existing technologies, technique of the present invention is simple, with short production cycle, be easy to large-scale production, pollution to environment is also less, and the Graphene preparing has porousness, the feature that specific surface area is large, can be widely used in lithium ion battery negative, electrode of super capacitor, carrier of photocatalyst, the every field such as sorbent material.
Preferably, the weight ratio of described organic acid and salt is 1: 10-10: 1.
Preferably, described non-oxidizing atmosphere is made up of one or more in nitrogen, argon gas, hydrogen and ammonia.
Preferably, due to porous graphene at high temperature contact with air be easy to oxidized, the problem such as product purity and Quality Down causing for fear of oxidation, the present invention is in the time of the metal oxide of removing in mixture, preferably in the following ways: under the condition of isolated air and/or mixture temperature adopt the mode of pickling to remove the metal oxide in mixture under lower than the condition of 100 DEG C, acid is selected from one or more in hydrochloric acid, nitric acid, sulfuric acid, acetic acid and oxalic acid.Preferred, one or both in employing 37% concentrated hydrochloric acid and 30% acetic acid, pickling 4-8 hour under the temperature condition of 40-60 DEG C.After pickling completes, further suction filtration is to being dried to obtain highly purified porous graphene.
Preferably, the speed of described heating is 0.5-15 DEG C/min.In the time that heating rate is too fast, the productive rate of porous graphene is lower, and excessively slow heating rate, can greatly extend again the production cycle of product.Preferred, the speed of described heating is 2-10 DEG C/min.
Preferably, in order to improve the quality product of porous graphene, the mixture of described organic acid and salt or organic salt are incubated 1-6h be heated to 400-1200 DEG C under non-oxidizing atmosphere after.
Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Embodiment 1, take 2 grams of calcium stearates, put it in magnetic boat, then in nitrogen, be warming up to 700 DEG C by the speed of 4 DEG C/min with tube furnace, 700 DEG C of heating 2 hours, obtain Graphene and calcium oxide mixture,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 2, take 2 grams of Zinc Gluconates, put it in magnetic boat, then in argon gas, be warming up to 600 DEG C by the speed of 2 DEG C/min with tube furnace, 600 DEG C of heating 2 hours, obtain Graphene and zinc oxide mixture,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 3, take 2 grams of Eighteen alkyl acid calcium, put it in magnetic boat, then in nitrogen, be warming up to 600 DEG C by the speed of 10 DEG C/min with tube furnace, 600 DEG C of heating 2 hours, obtain Graphene and calcium oxide mixture,, at 50 DEG C, wash 4 hours with 30% acetic acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 4, take 1 gram of zinc oleate, put it in magnetic boat, then use tube furnace at Ar/H
2in gas mixture, be warming up to 800 DEG C by the speed of 5 DEG C/min, 800 DEG C of heating 2 hours, obtain Graphene and zinc oxide mixture,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 5, take 1 gram of oleic acid and 1 gram of zinc acetate, put it in magnetic boat, then in nitrogen, be warming up to 800 DEG C by the speed of 5 DEG C/min with tube furnace, 800 DEG C of heating 2 hours, obtain Graphene and zinc oxide mixture,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 6, take 1 gram of gluconic acid and 1 gram of calcium acetate, put it in magnetic boat, then in nitrogen, be warming up to 400 DEG C by the speed of 5 DEG C/min with tube furnace, 400 DEG C of heating 6 hours, obtain Graphene and calcium oxide mixture,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 7, take 2 grams of gluconic acid barium, put it in magnetic boat, then in nitrogen, be warming up to 1200 DEG C by the speed of 5 DEG C/min with tube furnace, 1200 DEG C of heating 1 hour, obtain Graphene and Lithium Oxide 98min mixture,, at 50 DEG C, wash 4 hours with 30% the sulfuric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 8, take 2 grams of manganese citrates, put it in magnetic boat, then in nitrogen, be warming up to 1200 DEG C by the speed of 5 DEG C/min with tube furnace, 1200 DEG C of heating 2 hours, obtain Graphene and manganese monoxide mixture,, at 50 DEG C, wash 4 hours with 30% the acetic acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 9, take 3 grams of threonic acid calciums and 3 grams of calglucons, put it in magnetic boat, then in nitrogen, be warming up to 1200 DEG C by the speed of 5 DEG C/min with tube furnace, 1200 DEG C of heating 2 hours, obtain Graphene and calcium oxide mixture,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 10, take 1 gram of citrate of lime and 4 grams of calcium lactates, put it in magnetic boat, then in nitrogen, be warming up to 1000 DEG C by the speed of 5 DEG C/min with tube furnace, 1000 DEG C of heating 2 hours, obtain Graphene and manganese monoxide mixture,, at 50 DEG C, wash 4 hours with 30% the acetic acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 11, take 1 gram of gluconic acid and 1 gram of calcium chloride, put it in magnetic boat, then in nitrogen, be warming up to 400 DEG C by the speed of 5 DEG C/min with tube furnace, 400 DEG C of heating 6 hours, obtain Graphene and calcium oxide composite,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 12, take 1 gram of gluconic acid and 1.5 grams of zinc iodides, put it in magnetic boat, then in argon gas, be warming up to 600 DEG C by the speed of 2 DEG C/min with tube furnace, 600 DEG C of heating 2 hours, obtain Graphene and zinc oxide composites,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 13, take 1 gram of gluconic acid and 1.5 grams of barium bromides, put it in magnetic boat, then in nitrogen, be warming up to 600 DEG C by the speed of 10 DEG C/min with tube furnace, 600 DEG C of heating 2 hours, obtain Graphene and calcium oxide composite,, at 50 DEG C, wash 4 hours with 30% acetic acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 14, take 1 gram of gluconic acid and 1.5 grams of magnesium nitrates, put it in magnetic boat, then in nitrogen, be warming up to 600 DEG C by the speed of 10 DEG C/min with tube furnace, 600 DEG C of heating 2 hours, obtain Graphene and calcium oxide composite,, at 50 DEG C, wash 4 hours with 30% acetic acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 15, take 0.25 gram of D-VB5 and 2.5 grams of zinc iodides, put it in magnetic boat, then in argon gas, be warming up to 600 DEG C by the speed of 2 DEG C/min with tube furnace, 600 DEG C of heating 2 hours, obtain Graphene and zinc oxide composites,, at 50 DEG C, wash 4 hours with 37% concentrated hydrochloric acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
Embodiment 16, take 2.5 grams of gluconic acids and 0.25 gram of nickel acetate, put it in magnetic boat, then in nitrogen, be warming up to 600 DEG C by the speed of 10 DEG C/min with tube furnace, 600 DEG C of heating 2 hours, obtain Graphene and calcium oxide composite,, at 50 DEG C, wash 4 hours with 30% acetic acid of 10 milliliters, suction filtration, to dry, can obtain porous graphene.
The porous graphene that above-described embodiment 1-16 is prepared and the mixture of metal oxide and the porous graphene finally obtaining, carry out electron-microscope scanning, shown in the scanning electron microscope (SEM) photograph obtaining can see figures.1.and.2.Wherein, Figure 1 shows that porous graphene that embodiment 1 prepares and the scanning electron microscope (SEM) photograph of calcium oxide mixture, Figure 2 shows that the scanning electron microscope (SEM) photograph of the porous graphene that embodiment 1 prepares.Known as shown in Figure 1, in the porous graphene that the present invention prepares and the mixture of metal oxide, porous graphene coated metal oxide (what present particle is exactly metal oxide, sheet be Graphene, the metal oxide shown in Fig. 1 is calcium oxide).Known as shown in Figure 2, the Graphene that the present invention finally prepares presents cell texture.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes specification sheets of the present invention and accompanying drawing content to do; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (9)
1. a porous graphene preparation method, is characterized in that, comprising:
The mixture of organic acid and salt or organic salt are heated to 350-1600 DEG C under non-oxidizing atmosphere, obtain the mixture of porous graphene and metal oxide;
Remove the metal oxide in mixture, obtain porous graphene;
Wherein, described organic salt is selected from one or more in alkyl soap and the oleate that Citrate trianion, gluconate, tartrate, D-VB5 salt, threose acid salt, the carbonatoms of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth are 8-24;
Wherein, described organic acid is selected from one or more in alkyl lipid acid and the oleic acid that citric acid, gluconic acid, tartrate, D-VB5, threonic acid, carbonatoms are 8-24;
Wherein, described salt is selected from one or more in acetate, nitrate, chlorate, Bromide and the iodized salt of magnesium, calcium, strontium, barium, cobalt, nickel, manganese, iron, zinc, aluminium, indium or bismuth.
2. porous graphene preparation method according to claim 1, is characterized in that: the weight ratio of described organic acid and salt is 1: 10-10: 1.
3. porous graphene preparation method according to claim 1, is characterized in that: the mixture of described organic acid and salt or organic salt are incubated 1-6h be heated to 400-1200 DEG C under non-oxidizing atmosphere after.
4. porous graphene preparation method according to claim 1, is characterized in that: under the condition of isolated air and/or mixture temperature adopt the mode of pickling to remove the metal oxide in mixture under lower than the condition of 100 DEG C.
5. porous graphene preparation method according to claim 4, is characterized in that: described acid is selected from one or more in hydrochloric acid, nitric acid, acetic acid and oxalic acid.
6. porous graphene preparation method according to claim 1, is characterized in that: described non-oxidizing atmosphere is made up of one or more in nitrogen, argon gas, hydrogen and ammonia.
7. porous graphene preparation method according to claim 1, is characterized in that: the speed of described heating is 0.5-15 DEG C/min.
8. porous graphene preparation method according to claim 7, is characterized in that: the speed of described heating is 2-10 DEG C/min.
9. the porous graphene being prepared by the preparation method described in claim 1 to 8 any one.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN105502359A (en) * | 2015-12-22 | 2016-04-20 | 福州大学 | Preparation method of low-cost porous graphene |
| WO2017172800A1 (en) * | 2016-03-28 | 2017-10-05 | Board Of Regents, The University Of Texas System | Low-temperature pyrolysis of organic acid salts providing graphene rich carbons |
| CN108520828A (en) * | 2018-04-02 | 2018-09-11 | 桂林电子科技大学 | A kind of high-graphitized more hole carbon nanosheet preparation method and application of two dimension |
| CN109368620A (en) * | 2018-12-11 | 2019-02-22 | 中国科学院兰州化学物理研究所 | A kind of preparation method of extra small sub-nanometer hole porous graphene |
| CN109534327A (en) * | 2019-01-28 | 2019-03-29 | 哈尔滨工业大学（威海） | A kind of preparation method of graphene |
| CN109773213A (en) * | 2019-01-28 | 2019-05-21 | 哈尔滨工业大学（威海） | A kind of preparation method of graphene/copper composite nano plate |
| CN111547705A (en) * | 2020-05-12 | 2020-08-18 | 中国计量大学 | Preparation method of porous carbon electrode material |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN102897756A (en) * | 2012-09-19 | 2013-01-30 | 电子科技大学 | Preparation method of graphene |
| CN102910624A (en) * | 2012-11-08 | 2013-02-06 | 南京师范大学 | Preparation method of high-yield graphene without defects |
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| CN103539104A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene quantum dot dispersion |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
-
2014
- 2014-07-25 CN CN201410361303.6A patent/CN104108709A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701187A (en) * | 2011-07-13 | 2012-10-03 | 华东理工大学 | Preparation method of graphene and graphene prepared by same |
| CN102431999A (en) * | 2011-09-22 | 2012-05-02 | 中国科学院金属研究所 | Method for preparing high-quality graphene |
| CN102897756A (en) * | 2012-09-19 | 2013-01-30 | 电子科技大学 | Preparation method of graphene |
| CN102910624A (en) * | 2012-11-08 | 2013-02-06 | 南京师范大学 | Preparation method of high-yield graphene without defects |
| CN103332688A (en) * | 2013-07-16 | 2013-10-02 | 中国科学院山西煤炭化学研究所 | Method for synthesizing graphene with organic acid metal salt |
| CN103539104A (en) * | 2013-10-22 | 2014-01-29 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene quantum dot dispersion |
| CN103601177A (en) * | 2013-11-19 | 2014-02-26 | 中国科学院山西煤炭化学研究所 | Method for preparing graphene from solid organic acid by using alkali metal salt as catalyst |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| CN105502359A (en) * | 2015-12-22 | 2016-04-20 | 福州大学 | Preparation method of low-cost porous graphene |
| WO2017172800A1 (en) * | 2016-03-28 | 2017-10-05 | Board Of Regents, The University Of Texas System | Low-temperature pyrolysis of organic acid salts providing graphene rich carbons |
| US10968105B2 (en) | 2016-03-28 | 2021-04-06 | Board Of Regents, The University Of Texas System | Low-temperature pyrolysis of organic acid salts providing graphene rich carbons |
| CN108520828A (en) * | 2018-04-02 | 2018-09-11 | 桂林电子科技大学 | A kind of high-graphitized more hole carbon nanosheet preparation method and application of two dimension |
| CN109368620A (en) * | 2018-12-11 | 2019-02-22 | 中国科学院兰州化学物理研究所 | A kind of preparation method of extra small sub-nanometer hole porous graphene |
| CN109534327A (en) * | 2019-01-28 | 2019-03-29 | 哈尔滨工业大学（威海） | A kind of preparation method of graphene |
| CN109773213A (en) * | 2019-01-28 | 2019-05-21 | 哈尔滨工业大学（威海） | A kind of preparation method of graphene/copper composite nano plate |
| CN111547705A (en) * | 2020-05-12 | 2020-08-18 | 中国计量大学 | Preparation method of porous carbon electrode material |
| CN111547705B (en) * | 2020-05-12 | 2022-03-29 | 中国计量大学 | Preparation method of porous carbon electrode material |
| CN112301731A (en) * | 2020-11-03 | 2021-02-02 | 江苏科技大学 | Heat-conducting nylon 6/graphene composite fiber and preparation method thereof |
| CN112301731B (en) * | 2020-11-03 | 2022-12-27 | 江苏科技大学 | Heat-conducting nylon 6/graphene composite fiber and preparation method thereof |
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Inventor after: Guo Wei Inventor after: Ma Jianmin Inventor after: Mao Yuhua Inventor before: Ma Jianmin Inventor before: Mao Yuhua |
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Application publication date: 20141022 |
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| RJ01 | Rejection of invention patent application after publication |