CN105609790A - Preparation method for Ni-Co/carbon nanotube aerogel catalyst of zinc-air battery - Google Patents
Preparation method for Ni-Co/carbon nanotube aerogel catalyst of zinc-air battery Download PDFInfo
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- CN105609790A CN105609790A CN201510943911.2A CN201510943911A CN105609790A CN 105609790 A CN105609790 A CN 105609790A CN 201510943911 A CN201510943911 A CN 201510943911A CN 105609790 A CN105609790 A CN 105609790A
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- sodium alginate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 6
- 239000004964 aerogel Substances 0.000 title abstract description 4
- 229910017709 Ni Co Inorganic materials 0.000 title abstract 3
- 229910003267 Ni-Co Inorganic materials 0.000 title abstract 3
- 229910003262 Ni‐Co Inorganic materials 0.000 title abstract 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000661 sodium alginate Substances 0.000 claims abstract description 27
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 27
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 18
- 239000011701 zinc Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 235000010443 alginic acid Nutrition 0.000 claims description 9
- 229920000615 alginic acid Polymers 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- 229960001126 alginic acid Drugs 0.000 claims description 8
- 239000000783 alginic acid Substances 0.000 claims description 8
- 150000004781 alginic acids Chemical class 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 230000005518 electrochemistry Effects 0.000 claims description 2
- 239000000017 hydrogel Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 3
- 238000005121 nitriding Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 abstract description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method for a Ni-Co/carbon nanotube aerogel catalyst of a zinc-air battery, which is used for the field of the zinc-air battery. In the catalyst, the nanometer Ni-Co/carbon nanotube aerogel dual-functional catalyst is successfully prepared by taking sodium alginate, cobalt chloride hexahydrate, nickel chloride hexahydrate and carbon nanotubes as raw materials. The dual-functional catalyst is endowed with excellent oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalytic performance, the initial potential of OER is early, the current density of the dual-functional catalyst is large, the initial potential of ORR is early, the limiting current density is large, and the stability is high; and moreover, the charging and discharging voltage difference of the zinc-air battery before and after long circulation test is small, and the energy efficiency after long circulation is high. The preparation method has the advantages of simplicity, rapidness in operation, greenness and environment friendliness, the source of sodium alginate is rich, and the obtained dual-functional catalyst is excellent in performance and is the zinc-air battery catalyst having a very good prospect.
Description
Technical field
The invention belongs to zinc and air cell field, be specifically related to a kind of preparation method of nanometer nickel-cobalt/CNT aeroge zinc and air cell catalyst。。
Background technology
It is a kind of that metal-air battery is considered toNovel, the energy conversion device of non-environmental-pollution, and its usefulness is significantly higher than traditional generator, and zinc-air battery shows good application prospect in recent years. But zinc-air battery will reach the problem such as cost and performance that real commercial applications also needs to solve ORR and OER catalyst. Ruthenium, iridium and platinum group catalyst are the most frequently used catalyst of cash, but the factor such as it is expensive, rare, poor stability has seriously limited the application and development of zinc and air cell. Therefore, development is a kind ofNovel, wide material sources zinc and air cell catalyst be the difficulty that must capture for the large-scale application that realizes zinc and air cell.
Sodium alginate, as a kind of marine biomass macromolecule, from brown alga, extract, aboundresources, to be formed by connecting by 1-4 glycosidic bond by beta-D-mannuronic acid (being called for short M) and α-L-guluronic acid (being called for short G), the difference of the two is the difference of the upper carboxyl of C-5 position, the structural formula of two kinds of uronic acidsSuc as formula aShown in. The exclusive feature of alginate is when running into bivalent metal ion, as nickel ion and cobalt ions, can form gel, and this gel structure is described to " Egg tray structure ",Suc as formula bShown in, a lot of application of sodium alginate are all based on this special character.
Specific surface area of carbon nanotube is large, electric conductivity is good, stable chemical performance, and catalyst granules is had to very strong adhesive ability, and these excellent performances are all beneficial to the reaction in zinc and air cell, and therefore, CNT can be used as a good carbon carrier. But also there are a lot of shortcoming and defect in CNT itself, such as CNT easily tangles, and aeroge can address these problems, because the three-dimensional structure of aeroge can effectively stop the winding of CNT, thereby maintain its high-specific surface area and excellent performance, and then can play better catalytic action to zinc and air cell.
Summary of the invention
The present invention utilizes the abundant sodium alginate in source as raw material, has prepared and has had very high OER and the bifunctional nanometer nickel-cobalt/CNT of ORR aeroge.
Preparation process of the present invention is simple, does not need expensive device, and products obtained therefrom quality high-performance is good, has bright prospect in the large-scale application of zinc and air cell in future.
A preparation method for nanometer nickel-cobalt/CNT aeroge zinc and air cell catalyst, manufacturing process comprises the following steps:
1) with the sodium alginate soln of secondary deionized water preparation 1～3wt%, stir the sodium alginate soln that obtains mixing 4～6 hours;
2) to adding CNT (sodium alginate and CNT mass ratio are about 25: 1～2: 1) in above-mentioned sodium alginate soln, stir 4～6 hours, obtain the mixed liquor that sodium alginate and CNT mix;
3) preparation mass fraction is the nickel cobalt mixed solution of 5wt%, the mixing secondary deionized water solution (sodium alginate and nickel chloride/cobalt chloride mass ratio are 1: 5) of nickel chloride and cobalt chloride, stirring is fully dissolved it, and wherein nickel and cobalt ions mol ratio are 1: 1 or 1: 2.
4) mixed liquor of sodium alginate and CNT is splashed in above-mentioned nickel chloride and cobalt chloride mixed solution and forms gel, after having splashed into, leave standstill 2 hours;
5) above-mentioned gel is separated, and is cleaned repeatedly with secondary deionized water concussion, until in cleaning fluid without the existence of free state nickel and cobalt ions, after having cleaned, put it into 12 hours formation aeroges of freeze drying in freeze drier;
6) above-mentioned aeroge is put into tube furnace and calcine, in ammonia atmosphere, calcine 1～2 hour for 700 DEG C, then 400 DEG C of oxidations obtain end product nanometer nickel-cobalt/CNT aeroge zinc and air cell catalyst for 1～2 hour in air;
7) test OER and the ORR performance of above-mentioned product by electrochemical workstation and rotating disk electrode (r.d.e), by the zinc and air cell performance of blue electrical testing product.
The present invention has the following advantages:
The raw material that the present invention uses is mainly sodium alginate, and sodium alginate extracts from marine alga, wide material sources, environment-friendly and green, safe.
Nanometer nickel-cobalt/CNT aeroge prepared by the inventive method, there is very high oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) performance, its OER take-off potential (1.43VvsRHE) in 1MKOH electrolyte is more early than the Ir/C of business (1.485VvsRHE), and current density reaches 10mA/cm2Corresponding voltage is that 1.465V is more Zao than Ir/C1.554V.
Its ORR wave inception electromotive force (0.89VvsRHE), limiting current density (4.88mA/cm2), it is more stable than business Pt/C (current density reduces > 20%) that stability aspect 21600s after-current density reduces < 9%.
And in zinc and air cell test when current rate 5A/g charging and discharging voltage be respectively～1.95 and～voltage difference of 1.20V charging and discharging is 0.75V, charging and discharging voltage after circulation 70 circles is respectively～1.94 and～voltage difference of 1.14V charging and discharging is 0.8V, the energy efficiency after long circulation is 58.5%.
Nanometer nickel-cobalt/CNT aeroge prepared by the inventive method can synthesize in a large number, does not need expensive device, can be widely used in zinc and air cell.
Brief description of the drawings
Fig. 1Nanometer nickel-cobalt/CNT aeroge XRD and the TEM that specific embodiment 1,2 obtainsFigure。
Fig. 2It is the catalytic performance sign that specific embodiment 1,2 obtains nanometer nickel-cobalt/CNT aeroge
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment mono-
0.404g sodium alginate is dissolved in 40g secondary deionized water solution, stirs 6 hours, and the sodium alginate soln of the 1wt% that obtains mixing, is designated as solution 1. 0.0161g CNT is sneaked in the sodium alginate soln of above-mentioned preparation, stir 6 hours, obtain the mixed solution of sodium alginate CNT, be designated as solution 2. 1.3g Nickel dichloride hexahydrate and 1.3g cobalt chloride hexahydrate are dissolved in 50g secondary deionized water solution, obtain nickel chloride and cobalt chloride mixed solution, be designated as solution 3. Solution 2 is splashed in nickel chloride and cobalt chloride mixed solution in ie in solution 3, form the hydrogel of alginic acid nickel cobalt CNT, after having splashed into, leave standstill 2 hours. Alginic acid nickel cobalt CNT gel obtained above is separated, and with secondary deionized water clean, until by solution without free state nickel and cobalt ions. The alginic acid nickel cobalt CNT gel obtaining after cleaning is put into freeze drier freeze drying 12 hours, obtain alginic acid nickel cobalt CNT aeroge. Alginic acid nickel cobalt CNT aeroge is put into tube furnace and carry out carbonization, in ammonia atmosphere, calcine 1 hour for 700 DEG C; In air, 400 DEG C of oxidations obtain nano nickel/nickel oxide/cobalt acid nickel/CNT aerogel catalyst for 1 hour again. Utilize electrochemical workstation, rotating disk electrode (r.d.e) and blue electricity to carry out electrochemistry and zinc and air cell test above-mentioned obtained end product nano nickel/nickel oxide/cobalt acid nickel/CNT aeroge zinc and air cell catalyst.
Embodiment bis-
Except 0.1616g CNT being sneaked in the sodium alginate soln of above-mentioned preparation, stir 6 hours, obtain the mixed solution of sodium alginate CNT, be designated as solution 2. All the other steps are all identical with embodiment 1.
Claims (7)
1. a preparation method for nickel cobalt/CNT aeroge zinc and air cell catalyst, is characterized in that described method comprises following stepRapid:
1) preparation sodium alginate secondary deionized water solution, joins a certain amount of CNT in this solution, and stirs,Obtain the mixed solution of sodium alginate CNT;
2) above-mentioned mixed solution is splashed in the secondary deionized water solution of cobalt chloride and nickel chloride mixing, form alginic acid nickel cobalt/carbonNanotube hydrogel, separates, and cleans until without free state nickel ion and cobalt ions existence, then will by secondary deionized waterIt is put into freeze drier freeze drying and obtains alginic acid nickel cobalt/CNT aeroge;
3) alginic acid nickel cobalt/CNT aeroge, through certain carbonization and oxidation technology calcining in tube furnace, obtains nano nickel/nickel oxide/ cobalt acid nickel/CNT aeroge bifunctional catalyst;
4) empty electric with electrochemistry and the zinc of electrochemical workstation, rotating disk electrode (r.d.e), rotating ring disk electrode (r.r.d.e) and the above-mentioned product of blue electrical testingPond performance.
2. according to the preparation method described in claims 1, it is characterized in that step 1) described in the concentration of sodium alginate soln be1～3wt%, when wherein sodium alginate soln concentration is 1wt%, chemical property is best.
3. preparation method according to claim 1, is characterized in that step 1) described in mixing time be 4～6h.
4. preparation method according to claim 1, is characterized in that step 1) described in sodium alginate and CNTIn mixed solution the mass ratio of sodium alginate and CNT be about 25: 1～2: 1.
5. preparation method according to claim 1, is characterized in that step 2) described in sodium alginate and nickel chloride/chlorineChanging cobalt mass ratio is 1: 5.
6. preparation method according to claim 1, is characterized in that step 2) described in nickel chloride and cobalt chloride mix twoInferior deionized water solution mass fraction is 5wt%, and wherein nickel and cobalt ions mol ratio are 1: 1 or 1: 2.
7. preparation method according to claim 1, is characterized in that step 3) described in nitriding process be in ammonia atmosphereIn 700 DEG C calcining 1～2 hour; Oxidation technology be in air atmosphere 400 DEG C calcining 1～2 hour.
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| CN201510943911.2A CN105609790B (en) | 2015-12-14 | 2015-12-14 | A kind of preparation method of nickel cobalt/carbon nanotube aerogel zinc and air cell catalyst |
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| CN201510943911.2A CN105609790B (en) | 2015-12-14 | 2015-12-14 | A kind of preparation method of nickel cobalt/carbon nanotube aerogel zinc and air cell catalyst |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106902715A (en) * | 2017-03-27 | 2017-06-30 | 中国科学院深圳先进技术研究院 | A kind of three-dimensional structure composite aerogel, Preparation Method And The Use |
| CN106910903A (en) * | 2017-02-23 | 2017-06-30 | 新乡医学院 | A kind of preparation method of nickel cobalt carbon nanotube aerogel zinc and air cell catalyst |
| CN107369840A (en) * | 2017-08-31 | 2017-11-21 | 华中科技大学 | A kind of atom level disperses the preparation method of non-noble metal fuel cell cathod catalyst |
| CN107910565A (en) * | 2017-10-26 | 2018-04-13 | 青岛大学 | A kind of preparation method of monatomic cobalt/graphene catalyst of fuel batter with proton exchange film |
| CN108682868A (en) * | 2018-03-21 | 2018-10-19 | 上海理工大学 | A kind of preparation method and application of carbon nanotube loaded transition metal oxide material |
| CN108987702A (en) * | 2018-07-16 | 2018-12-11 | 西安交通大学苏州研究院 | Integrated electrode material and its preparation and application based on composite aerogel |
| CN110265677A (en) * | 2019-07-01 | 2019-09-20 | 苏州工业职业技术学院 | A kind of S- doped carbon nanometer pipe composite material that NiCo@NiS inlays and its preparation and application |
| CN111341922A (en) * | 2018-12-19 | 2020-06-26 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
| CN111653789A (en) * | 2020-06-17 | 2020-09-11 | 泰州市海创新能源研究院有限公司 | Zinc-air battery catalyst and preparation method thereof |
| CN111785977A (en) * | 2020-06-04 | 2020-10-16 | 南京绿源智慧科技有限公司 | Preparation method of iron-cobalt alloy/nitrogen co-doped carbon aerogel electrode material |
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| CN115722242A (en) * | 2021-08-27 | 2023-03-03 | 上海交通大学 | Preparation method of mesoporous carbon nano composite catalytic material simultaneously loaded with transition metal monoatomic atoms and metallic nano particles |
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