AU2020201235B1 - Self-supporting nickel nanotubes on nickel foam as electrode materials for supercapacitors and preparation method thereof - Google Patents
Self-supporting nickel nanotubes on nickel foam as electrode materials for supercapacitors and preparation method thereof Download PDFInfo
- Publication number
- AU2020201235B1 AU2020201235B1 AU2020201235A AU2020201235A AU2020201235B1 AU 2020201235 B1 AU2020201235 B1 AU 2020201235B1 AU 2020201235 A AU2020201235 A AU 2020201235A AU 2020201235 A AU2020201235 A AU 2020201235A AU 2020201235 B1 AU2020201235 B1 AU 2020201235B1
- Authority
- AU
- Australia
- Prior art keywords
- nickel
- zinc oxide
- self
- supporting
- nickel foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 309
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 181
- 239000006260 foam Substances 0.000 title claims abstract description 82
- 239000002071 nanotube Substances 0.000 title claims abstract description 50
- 239000007772 electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 170
- 239000011787 zinc oxide Substances 0.000 claims abstract description 70
- 239000002073 nanorod Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000011258 core-shell material Substances 0.000 claims abstract description 32
- 238000004070 electrodeposition Methods 0.000 claims abstract description 29
- 238000005530 etching Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 29
- 239000007864 aqueous solution Substances 0.000 claims description 17
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 2
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a method for preparing a self-supporting nickel
nanotube on nickel foam as electrode materials for supercapacitors, comprising the
following steps: pretreating a nickel foam; growing zinc oxide nanorods on the
surface of the pretreated nickel foam by hydrothermal method or electrodeposition
method; electrodepositing an elemental nickel layer on the surface of the zinc oxide
nanorods to obtain a zinc oxide @ nickel core-shell structure; and finally calcining
and etching the zinc oxide @ nickel core-shell structure. The preparation process of
the present invention is convenient and simple, green and environmentally friendly,
low in cost, and solves the problems in the traditional processes such as excessive
impurities in materials and tedious operation, and constructs a novel supercapacitor
energy storage material containing nickel nanotubes from another direction. In
addition, the nickel nanotubes grown on the surface of nickel foam according to the
present invention are used as a self-supporting electrode material with good
conductivity and stable structure, and the hollow tubular structure can provide a larger
specific surface area, thereby the charge-discharge cycle stability of the entire
capacitor can be ensured while the conductive performance is improved.
Description
TECHNICAL FIELD The present invention relates to the field of electrode materials for supercapacitors, in particular to self-supporting nickel nanotubes on nickel foam as electrode materials for supercapacitors and preparation method thereof.
BACKGROUND Supercapacitors are novel energy storage devices between traditional capacitors and rechargeable batteries with both fast charging and discharging characteristics of capacitors and energy storage characteristics of batteries. Compared with traditional capacitors, they have merits such as high power density, long cycle life, broad operating temperature range, and being maintenance-free and environment-friendly. They are mainly used in high-power pulse applications and instantaneous power keeping, and can be quickly charged and discharged and maintain stability. The superior performance of supercapacitors depends entirely on the choice of electrode material. Although previous studies have showed that gold and platinum electrodes have good test properties in experiments, they are too expensive to use extensively. Elemental nickel has good stability only second to platinum and gold, and has good conductivity as well as low price, so it is a good choice. Therefore, after considering the overall performance of elemental nickel, the inventors have selected it as a self-supporting electrode material for supercapacitors and doped it with other active materials so as to prepare novel supercapacitors.
SUMMARY OF THE PRESENT INVENTION With respect to the problems in the prior art, the first aspect of the present invention is to provide a self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors and a preparation method thereof. The single layer of nickel nanotubes prepared in the present invention is grown on a nickel foam and is used as a conductive frame for supercapacitors, thereby improving the conductive performance while ensuring the charge-discharge cycle stability of the entire capacitor. With respect to the first aspect, the present invention adopts the following technical solutions: A method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors, comprising the following steps: growing zinc oxide nanorods on the surface of a nickel foam by hydrothermal method or electrodeposition method; electrodepositing an elemental nickel layer on the surface of the zinc oxide nanorods to obtain a zinc oxide @ nickel (ZnO@Ni)core-shell structure; and calcining and etching the zinc oxide @ nickel core-shell structure to obtain the self-supporting nickel nanotubes based on nickel foam as electrode materials for.supercapacitors. Further, in the above technical solution, the nickel foam is pretreated before growing zinc oxide nanorods on the surface of the nickel foam. Further, in the above technical solution, the zinc oxide nanorods have a thickness of 200-300 nm. Further, in the above technical solution, the elemental nickel layer has a thickness of 5-50 nm, and preferably 10-20 nm. Further, in the above technical solution, the calcination temperature and time of the zinc oxide @ nickel core-shell structure are 350-400 °C and 1-3 h, respectively. Further, in the above technical solution, the etching comprises using a low-concentration acid or base solution to remove zinc oxide core from the zinc oxide @ nickel core-hell structure so as to form a nickel nanotube structure. Preferably, in the above technical solution, the etching is carried out in a 2 mol/L KOH solution at room temperature for 5-7 h. Further, in the above technical solution, the process for growing zinc oxide nanorods on the surface of the nickel foam by hydrothermal method comprises following steps: (a) preparation of zinc oxide seed layer: the pretreated nickel foam is soaked in an anhydrous methanol aqueous solution containing 0.025-0.03mol/L zinc acetate, ultrasonically stirred for 10-30 min, taken out, annealed at 150-300°C for 1-2 h, and cooled naturally to obtain a zinc oxide seed layer; (b) preparation of zinc oxide growth layer: zinc salt aqueous solution and hexamethylenetetramine aqueous solution of same mole concentration and equal volume are mixed well and transferred to a reaction kettle; the nickel foam with the seed layer obtained in step (1) is vertically upward placed in the reaction kettle, and ammonia water is dropped in, then the reaction kettle is sealed and heated to
80-100°C, and the reaction is carried out at constant temperature for 8-12h; upon the completion of the reaction, the resultant is cooled, cleaned and dried to obtain a zinc oxide nanorod array. Preferably, in the above technical solution, the zinc salt in step (b) is any one of zinc acetate, zinc nitrate, zinc chloride and the like. Preferably, in the above technical solution, the zinc oxide seed layer in step (a) has a thickness of 1-10 nm, and preferably 5 nm. Preferably, in the above technical solution, the molar concentration of the zinc salt aqueous solution in step (b) is 0.005 to 0.1 mol/L; the molar concentration of the hexamethylenetetramine aqueous solution is 0.005 to 0.1 mol/L. Preferably, in the above technical solution, the mass percentage of the ammonia water in step (b) is 25-28%. Further, in the above technical solution, the process for growing zinc oxide nanorods on the surface of nickel foam by electrodeposition method is as follows: Electrodeposition is conducted in a mixed aqueous solution of zinc nitrate and ammonium nitrate as an electrolyte, at a constant temperature of 60-80°C and at a constant current of 10-15 mA for 60-100 min using a three-electrode system, namely, nickel foam as working electrode, platinum electrode or graphite electrode as counter electrode, and saturated calomel electrode as reference electrode, and then the working electrode is cleaned and dried to obtain zinc oxide nanorods. Further, in the above technical solution, the zinc oxide @ nickel core-shell structure can be prepared by potentiostatic electrodeposition method or galvanostatic electrodeposition method. Preferably, in the above technical solution, the process for preparing the zinc oxide @ nickel core-shell structure by potentiostatic electrodeposition method is as follows: Potentiostatic electrodeposition is conducted in a mixed aqueous solution of nickel chloride, ammonium chloride and sodium chloride of same molar concentration as an electrolyte at room temperature using a three-electrode system, namely, the nickel foam with zinc oxide nanorods grown thereon as working electrode, platinum electrode or graphite electrode as counter electrode, and saturated calomel electrode as reference electrode; upon the completion of the electrodeposition, the working electrode is cleaned and dried to obtain zinc oxide @ nickel core-shell structure. More preferably, in the above technical solution, the potentiostatic electrodeposition time is not limited, and may be determined according to the thickness of the elemental nickel layer to be deposited on the surface of the zinc oxide nanorods, for example, 5 min, 10 min, 15 min, or 20 min. More preferably, in the above technical solution, the deposition potential used in the potentiostatic method is -1.6 to -2.7V. Preferably, in the above technical solution, the process for preparing the zinc oxide @ nickel core-shell structure by galvanostatic electrodeposition method is as follows: Galvanostatic electrodeposition is conducted in a mixed aqueous solution of nickel sulfate and ammonium chloride as an electrolyte at room temperature using a three-electrode system, namely, nickel foam with zinc oxide nanorods grown on the surface thereof as working electrode, platinum electrode or graphite electrode as counter electrode, and saturated calomel electrode as reference electrode; upon completion of the electrodeposition, the working electrode is cleaned and dried to obtain zinc oxide @ nickel core-shell structure. More preferably, in the above technical solution, the constant current used in the galvanostatic method is 0.5-8 mA. More preferably, in the above technical solution, the galvanostatic electrodeposition time is not limited, and may be determined according to the thickness of the elemental nickel layer to be deposited on the surface of the zinc oxide nanorods, for example, 20 min, 30 min, or 40 min. A second aspect of the present invention is to provide a self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors prepared by the method described above. A third aspect of the present invention is to provide use of the self-supporting nickel nanotubes on nickel foam prepared by the method described above in a self-supporting negative electrode material for supercapacitors. The principle of the invention is as follows: Zinc oxide nanorods are used as a template for depositing a layer of elemental nickel, and then etched by the characteristic that zinc oxide is soluble in acid or alkali solution while elemental nickel remains unchanged in the solution to react and prepare the nickel nanotube. Compared with the prior art, the self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors and the preparation method thereof according to the present invention have the following advantageous effects: (1) The nickel nanotubes grown on the surface of nickel foam according to the present invention are used as a self-supporting electrode material with good conductivity and stable structure, and the hollow tubular structure can provide a larger specific surface area. Moreover, the novel method for preparing the nickel form is cheap and simple. (2) The electrode material of the present invention is self-supporting and does not require additional conductive additives and binders, which optimizes the preparation process of electrode materials. (3) The single layer of nickel nanotubes prepared by the present invention is grown on the nickel foam and is used as a conductive support in preparing the supercapacitor electrode. Not any binder is used in the preparation process, so the problem of decreased cycle stability caused by swelling of the binder during discharge is prevented, and the charge-discharge cycle stability of the entire capacitor can be ensured while the conductive performance is improved.
BRIEF DESCRIPTION OF THE DRAWINGS Figures 1(a), (b), and (c) are SEM (scanning electron microscope) images of a ZnO nanorod array, a zinc oxide @ nickel core-shell structured nano-array, and nickel nanotubes obtained after etching, respectively, prepared according to Example 1 of the present invention; Figures 2(a), (b), and (c) are SEM images of a ZnO nanorod array, a zinc oxide @nickel core-shell structure, and nickel nanotubes, respectively, prepared according to Example 2 of the present invention; and Figure 3 is a schematic diagram of the structure of a zinc oxide @ nickel core-shell prepared on the surface of nickel foams according to the present invention.
DETAILED DESCRIPTION OF THE PRESENT INVENTION The above content of the present invention will be further illustrated in detail below in the form of embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following embodiments. Any technology implemented based on the above content of the present invention shall fall within the scope of the present invention. The self-supporting nickel nanotubes on nickel foam prepared by the method of the present invention are mainly used in a self-supporting negative electrode material for supercapacitors. The preparation process comprises: optionally cleaning a nickel foam substrate, and growing a zinc oxide nano-array and a ZnO @ Ni composite nanorod structure. Because of its stable physical and chemical properties and stable charge and discharge characteristics, elemental nickel is often used as a self-supporting negative electrode material in supercapacitors. The overall superiority of the battery can be improved by doping other active elements in nickel nanotubes. One of the preparation methods uses a hydrothermal method and a potentiostatic deposition method. Specifically, zinc acetate dihydrate (Zn(Ac) 2 •2H 2 0) and anhydrous methanol are used as a seed layer; zinc nitrate hexahydrate (Zn(NO) 3 •6H 20) and hexamethylenetetramine are used as growth solutions to grow zinc oxide nanorods on the surface of nickel foam, and a mixed solution of nickel chloride hexahydrate (NiCl 2•6H 20), ammonium chloride (NH 4 Cl) and sodium chloride (NaCl) is prepared to deposit elemental nickel on the surface of the zinc oxide nanorods. Another preparation method uses a galvanostatic deposition method. Specifically, electrodeposition is conducted in a mixed solution of 0.01 M zinc nitrate and 0.05 M ammonium nitrate at a constant temperature and a constant current to obtain zinc oxide nanorods; and then galvanostatic electrodeposition is conducted in a mixed solution of 0.01 M nickel sulfate and 0.015 M ammonium chloride at room temperature to obtain nickel nanotubes. The preparation process of the present invention is convenient and simple, green and environmentally friendly, low in cost, and solves the problems in the traditional processes such as excessive impurities in materials and tedious operation, and constructs a novel supercapacitor energy storage material containing nickel nanotubes from another direction. Example 1 In this example, the method for preparing a self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors comprises the following steps: (1) Pretreation of nickel foam A 3x4 cm2 nickel foam was prepared. The nickel form was immersed in 3 mol/L hydrochloric acid and ultrasonically cleaned for 15 min, and then ultrasonically cleaned in anhydrous ethanol for at least three times, and finally cleaned in deionized water for 15 min. The cleaned nickel foam was taken out and dried in a drying oven at 70°C for 8 h for use. (2) Preparation of zinc oxide nanorods (i) Preparation of zinc oxide seed layer 0.01 mol of zinc acetate was dissolved in 100 mL of anhydrous methanol, stirred for 15 min, and then the pretreated nickel foam from step (1) was immersed therein, ultrasonically stirred for 15 min. taken out and dried in a drying oven at 200°C for 1 h to obtain a zinc oxide seed layer having a thickness of about 5 nm. (ii) Preparation of a zinc oxide growth layer 0.1 mol of hexamethylenetetramine was dissolved in 100 mL of deionized water and mixed well, added with 0.1 mol of zinc nitrate hexahydrate (Zn (N0 3)•6H 2 0) and mixed well; 80 ml of the resulting mixture was put into a 100 mL polytetrafluoroethylene liner, droped with 560 L of 25% by mass of concentrated ammonia water, and then put into a stainless steel reaction kettle, heated to 90°C for hydrothermal reaction, and held at this temperature for 10 h to obtain a zinc oxide nanorod array having a thickness of 200-300 nm, which was then cleaned and dried for use. (3) Preparation of a zinc oxide @ nickel core-shell nano-array by potentiostatic electrodeposition Potentiostatic electrodeposition was conducted in a mixed aqueous solution of nickel chloride, ammonium chloride and sodium chloride of same molar concentration as an electrolyte at room temperature using a three-electrode system, namely, the nickel foam with zinc oxide nanorods grown thereon obtained in step (2) as working electrode, platinum electrode as counter electrode, and saturated calomel electrode as reference electrode. The composition of the electrolyte solution included 0.01 mol/L nickel chloride, 0.1 mol/L ammonium chloride and 0.1 mol/L sodium chloride. The potential was set to -1.8 V, and the deposition time was 15 min. Upon the completion of the reaction, the working electrode was cleaned and dried to obtain zinc oxide @ nickel core-shell structured nano-array for use, in which the zinc oxide nanorods were used as a substrate for cladding elemental nickel layer, and the thickness of the elemental nickel layer was about 15 nm. (4) Calcining The nickel foam of the ZnO/Ni core-shell structured nano-array obtained in step (3) was calcined at 350-400°C in a tube furnace under the introduction of argon gas containing 5% hydrogen for 90 min, cooled to room temperature, and taken out. (5) Etching A 2 mol/L potassium hydroxide aqueous solution was prepared, and the calcined core-shell nano-array from step (4) was put into the potassium hydroxide aqueous solution to react for 5 h, so that zinc oxide was fully dissolved. (6) Cleaning and drying The etched nickel foam was repeatedly soaked with deionized water, and dried in a drying oven for 8 h to obtain the self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors. Figures 1(a), (b), and (c) are SEM images of the ZnO nanorod array, the zinc oxide @ nickel core-shell structured nano-array, and the nickel nanotubes obtained after etching, respectively, prepared according to Example 1 of the present invention. ZnO is a direct wide-gap group II-VI semiconductor and has a hexagonal wurtzite structure, and ZnO crystal belongs to a hexagonal crystal system, so the morphology of the hexagonal prism-shaped ZnO nanorods prepared by hydrothermal method in this example was as shown in Fig. 1(a). Then a negative electric field was formed on the surface of the ZnO nanorods by negative potentiostatic electrodeposition. This negative electric field can attract nickel ions in the electrolyte solution and make them to deposit uniformly on the surface of each zinc oxide nanorod, thereby forming the zinc oxide @ nickel core-shell structured nano-array, and its morphology is shown in FIG. 1(b). Finally, by the characteristic that ZnO is soluble in low concentrations of acids or bases while nickel remains stable therein, ZnO was etched to obtain nickel nanotubes, and the structure of which was shown in Figure 1(c). Example 2 In this example, the method for preparing a self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors comprises the following steps: (1) Pretreation of nickel foam A 2.5x2.5 cm2 nickel foam was prepared. The nickel foam was immersed in 3mol/L hydrochloric acid and ultrasonically cleaned for 15 min, and then ultrasonically cleaned in anhydrous ethanol for at least three times, and finally cleaned in deionized water for 15 min. The cleaned nickel foam was taken out and dried in a drying oven at 70°C for 8 h for use. (2) Preparation of zinc oxide nanorods Electrodeposition was conducted in a mixed aqueous solution containing 0.01 mol/L zinc nitrate and 0.05 mol/L ammonium nitrate as an electrolyte at a constant temperature of 70°C and a constant current of 12.5 mA for 80 min using a three-electrode system, namely, the pretreated nickel foam from step (1) as working electrode, platinum electrode as counter electrode, and saturated calomel electrode as reference electrode. Then the working electrode was cleaned and dried to obtain zinc oxide nanorods having a thickness of 200-300 nm for use. (3) Preparation of a zinc oxide @ nickel core-shell nano-array by galvanostatic electrodeposition Electrodeposition was conducted in a mixed aqueous solution containing 0.01 mol/L nickel sulfate and 0.015 mol/L ammonium chloride as an electrolyte at room temperature and a constant current of 0.6 mA for 40 min using a three-electrode system, namely, the nickel foam with zinc oxide nanorods grown thereon obtained in step (2) as working electrode, platinum electrode as counter electrode, and saturated calomel electrode as reference electrode. Upon the completion of the electrodeposition, the working electrode was cleaned and dried to obtain zinc oxide @ nickel core-shell structured nano-array for use, in which the zinc oxide nanorods were used as a substrate for cladding elemental nickel layer, and the thickness of the elemental nickel layer was about 15 nm. (4) Calcining The nickel foam of the ZnO/Ni core-shell structured nano-array obtained in step (3) was calcined at 350-400°C in a tube furnace under the introduction of argon gas containing 5% hydrogen for 90 min, cooled to room temperature, and taken out. (5) Etching A 2 mol/L potassium hydroxide aqueous solution was prepared, and the calcined core-shell nano-array was put in the solution to react for 5-7 h, so that zinc oxide was fully dissolved. (6) Cleaning and drying The etched nickel foam was repeatedly soaked with deionized water, and dried in a drying oven for 8 h to obtain the self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors. Figures 2 (a), (b), and (c) are SEM images of the ZnO nanorod array, the zinc oxide @ nickel core-shell structured nano-array, and the nickel nanotubes, respectively, prepared according to this example. The growth mechanism and preparation process of the zinc oxide @ nickel core-shell structured nano-array were similar to those in Example 1, and will not be described in detail here. Example 3 In this example, the method for preparing a self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors comprises the following steps: (1) Pretreation of nickel foam A 2x2 cm2 nickel foam was prepared. The nickel foam was immersed in 3mol/L hydrochloric acid and ultrasonically cleaned for 15 min, and then ultrasonically cleaned in anhydrous ethanol for at least three times, and finally cleaned in deionized water for 15 min. The cleaned nickel foam was taken out and dried in a drying oven at 70°C for 8 h for use.
(2) Preparation of zinc oxide nanorods (i) Preparation of a zinc oxide seed layer 0.005 mol/L zinc acetate anhydrous ethanol solution was prepared and mixed well, and then the pretreated nickel foam from step (1) was immersed therein for 30 min, annealed in air at 350°C for 20 min to obtain a zinc oxide seed layer having a thickness of about 5 nm. (ii) Preparation of a zinc oxide growth layer The nickel foam with the seed layer grown thereon from step (i) was vertically placed in a 40 ml mixed solution prepared by equal volumes of 0.025mol/L zinc nitrate and 0.025 mol/L hexamethylenetetramine (HMTA; C 6H 12 N4 ), and then transferred to a 50 ml reaction kettle and subjected to hydrothermal reaction at a constant temperature of 95°C for 8 h. Upon the completion of the reaction, the resulting sample was cleaned and dried to obtain a uniform zinc oxide nanorod array with a thickness of 200-300 nm. (3) Preparation of a zinc oxide @ nickel core-shell nano-array Electrodeposition was conducted in a mixed aqueous solution of 0.02 mol/L nickel sulfate and 0.01 mol/L ammonium chloride as an electrolyte at room temperature and a constant current of 8 mA for 10 min using a three-electrode system, namely, the nickel foam with zinc oxide nanorods grown thereon obtained in step (2) as working electrode, platinum electrode as counter electrode, and saturated calomel electrode as reference electrode. Upon the completion of the electrodeposition, the working electrode was cleaned and dried to obtain the zinc oxide @ nickel core-shell structured nano-array, in which the zinc oxide nanorods were used as a substrate for cladding elemental nickel layer, and the thickness of the elemental nickel layer was about 15 nm. (4) Calcining The nickel foam of the ZnO/Ni core-shell structured nano-array obtained in step (3) was calcined at 350-400°C in a tube furnace under the introduction of argon gas containing 5% hydrogen for 90 min, cooled to room temperature, and taken out. (5) Etching A 2 mol/L potassium hydroxide aqueous solution was prepared, and the calcined core-shell nano-array was put in the solution to react for 5-7 h, so that zinc oxide was fully dissolved. (6) Cleaning and drying The etched nickel foam was repeatedly soaked with deionized water, and finally dried in a drying oven for 8 h, to obtain the self-supporting nickel nanotube on nickel foam as electrode materials for supercapacitors. Throughout the specification and the claims that follow, unless the context requires otherwise, the words "comprise" and "include" and variations such as "comprising" and "including" will be understood to imply the inclusion of a stated integer or group of integers, but not the exclusion of any other integer or group of integers. The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement of any form of suggestion that such prior art forms part of the common general knowledge.
Claims (15)
1. A method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors, comprising the following steps: growing zinc oxide nanorods on the surface of a nickel foam by hydrothermal method or electrodeposition method; electrodepositing an elemental nickel layer on the surface of the zinc oxide nanorods to obtain a zinc oxide @ nickel core-shell structure; and calcining and etching the zinc oxide @ nickel core-shell structure to obtain the self-supporting nickel nanotube based on nickel foam as electrode material for supercapacitor.
2. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to claim 1, wherein the nickel foam is pretreated before growing zinc oxide nanorods on the surface of the nickel foam.
3. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 2, wherein the zinc oxide nanorods have a thickness of 200-300 nm.
4. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 3, wherein the elemental nickel layer has a thickness of 5-50 nm.
5. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to claim 4, wherein the elemental nickel layer has a thickness of 10-20 nm.
6. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 5, wherein the calcination temperature and time of the zinc oxide @ nickel core-shell structure are 350-400°C and 1-3 h, respectively.
7. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 6, wherein the etching comprises using a low-concentration acid or base solution to remove a zinc oxide core from the zinc oxide @ nickel core-hell structure so as to form a nickel nanotube structure.
8. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 7, wherein the zinc oxide @ nickel core-shell structure is prepared by potentiostatic electrodeposition method or galvanostatic electrodeposition method.
9. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 8, wherein the deposition potential used in the potentiostatic method is -1.6 to -2.7V.
10. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 9, wherein the constant current used in the galvanostatic method is 0.5-8 mA.
11. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 10, wherein the step for growing zinc oxide nanorods on the surface of the nickel foam involves (a) preparation of a zinc oxide seed layer and (b) preparation of zinc oxide growth layer.
12. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to claim 11, wherein zinc acetate dihydrate (Zn(Ac) 2 •2H 20) and anhydrous methanol are used for preparation of the zinc oxide seed layer; zinc nitrate hexahydrate (Zn(NO) 3 •6H 20) and hexamethylenetetramine are used for preparation of the zinc oxide growth layer.
13. The method for preparing a self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors according to any one of claims 1 to 10, wherein the step for growing zinc oxide nanorods on the surface of the nickel foam is conducted by electrodeposition method using a mixed aqueous solution of zinc nitrate and ammonium nitrate as an electrolyte.
14. A self-supporting nickel nanotube on nickel foam as an electrode material for supercapacitors prepared by the method for preparing a self-supporting nickel nanotube on nickel foam as electrode material for supercapacitor according to any one of claims I to 13.
15. Use of the self-supporting nickel nanotube on nickel foam prepared by the method according to any one of claims 1 to 13 in a self-supporting negative electrode material for supercapacitors.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911013132.7A CN110729137A (en) | 2019-10-23 | 2019-10-23 | Foamed nickel self-supporting nickel nanotube supercapacitor electrode material and preparation method thereof |
| CN2019110131327 | 2019-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2020201235B1 true AU2020201235B1 (en) | 2020-08-06 |
Family
ID=69222903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2020201235A Active AU2020201235B1 (en) | 2019-10-23 | 2020-02-20 | Self-supporting nickel nanotubes on nickel foam as electrode materials for supercapacitors and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN110729137A (en) |
| AU (1) | AU2020201235B1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114216945A (en) * | 2021-12-14 | 2022-03-22 | 安徽大学 | Nickel-iron oxide composite material and preparation method and application thereof |
| CN114351177A (en) * | 2022-01-14 | 2022-04-15 | 西北工业大学 | Preparation method of self-supporting electrode based on ultrasonic chemical surface reconstruction |
| CN114582638A (en) * | 2022-03-01 | 2022-06-03 | 福建工程学院 | Method for preparing flexible porous nickel-cobalt-molybdenum-based supercapacitor electrode by electrochemically assisting etching template |
| CN114959768A (en) * | 2022-07-19 | 2022-08-30 | 清华大学 | Nickel-based oxygen evolution electrode, and preparation method and application thereof |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112090436B (en) * | 2020-09-14 | 2023-07-07 | 江浩 | Nickel-based catalyst, preparation method and application |
| CN112563039B (en) * | 2020-11-04 | 2022-03-15 | 中山大学 | Super capacitor electrode material, preparation method thereof and super capacitor |
| CN113257585A (en) * | 2021-05-13 | 2021-08-13 | 山东科技大学 | Metal hydroxide/zinc oxide electrode prepared by electrochemical deposition method and method thereof |
| CN113433171B (en) * | 2021-06-24 | 2022-11-22 | 兰州大学 | Gas sensitive material, gas sensor and preparation method and application of gas sensitive material |
| CN113594448A (en) * | 2021-07-05 | 2021-11-02 | 武汉科技大学 | Preparation method for directly constructing sulfur-doped iron-cobalt-nickel ternary oxide nanotube, product and application thereof |
| CN114525539B (en) * | 2022-03-17 | 2023-08-01 | 山东大学 | High-catalytic-activity and high-stability electric catalyst of marinolite sulfide, preparation method thereof and application thereof in electrolyzed water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876658A (en) * | 2017-03-28 | 2017-06-20 | 哈尔滨理工大学 | A kind of preparation method of Hollow Nickel rod/carbon ball array electrode |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108545961A (en) * | 2018-07-06 | 2018-09-18 | 合肥工业大学 | A kind of preparation method of nickel oxide nano pipe |
| CN109778249B (en) * | 2019-02-22 | 2020-05-22 | 浙江交通科技股份有限公司 | Preparation method for preparing metal core-shell nanowire |
-
2019
- 2019-10-23 CN CN201911013132.7A patent/CN110729137A/en active Pending
-
2020
- 2020-02-20 AU AU2020201235A patent/AU2020201235B1/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106876658A (en) * | 2017-03-28 | 2017-06-20 | 哈尔滨理工大学 | A kind of preparation method of Hollow Nickel rod/carbon ball array electrode |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114216945A (en) * | 2021-12-14 | 2022-03-22 | 安徽大学 | Nickel-iron oxide composite material and preparation method and application thereof |
| CN114351177A (en) * | 2022-01-14 | 2022-04-15 | 西北工业大学 | Preparation method of self-supporting electrode based on ultrasonic chemical surface reconstruction |
| CN114351177B (en) * | 2022-01-14 | 2023-05-26 | 西北工业大学 | Preparation method of self-supporting electrode based on ultrasonic chemistry surface reconstruction |
| CN114582638A (en) * | 2022-03-01 | 2022-06-03 | 福建工程学院 | Method for preparing flexible porous nickel-cobalt-molybdenum-based supercapacitor electrode by electrochemically assisting etching template |
| CN114582638B (en) * | 2022-03-01 | 2023-04-11 | 福建工程学院 | Method for preparing flexible porous nickel-cobalt-molybdenum-based supercapacitor electrode by electrochemically assisting etching template |
| CN114959768A (en) * | 2022-07-19 | 2022-08-30 | 清华大学 | Nickel-based oxygen evolution electrode, and preparation method and application thereof |
| CN114959768B (en) * | 2022-07-19 | 2022-10-21 | 清华大学 | Nickel-based oxygen evolution electrode, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110729137A (en) | 2020-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2020201235B1 (en) | Self-supporting nickel nanotubes on nickel foam as electrode materials for supercapacitors and preparation method thereof | |
| CN110364726B (en) | Preparation method and application of dual-ion doped vanadium pentoxide cathode material | |
| CN107275105B (en) | Electrode material for super capacitor and preparation method thereof | |
| CN111029160B (en) | Zinc-cobalt double-metal selenide nanosheet electrode and preparation method thereof | |
| WO2015103920A1 (en) | Multi-stage micro-nano structural material and preparation method therefor, and battery containing same | |
| CN110911174A (en) | Preparation method and application of NiCo-LDH nano material | |
| CN109244390B (en) | Phosphorus-doped lithium-rich manganese-based positive electrode material for lithium ion battery and preparation method thereof | |
| CN103489661B (en) | A kind of electrode material for super capacitor and preparation method thereof | |
| CN110931769B (en) | Preparation method of foamed nickel in-situ growth ternary cathode material, product and application | |
| CN108133831B (en) | Ni3S2Preparation method of @ rGO @ LDHs | |
| CN112072125A (en) | Preparation method and application of cobalt diselenide/carbon-based flexible electrode material with interface enhancement structure | |
| CN110350184B (en) | Preparation method of high-capacity NiMoO4 energy storage material for battery positive electrode material | |
| CN110993362A (en) | Novel three-dimensional electrode material, preparation method thereof and application thereof in super capacitor | |
| CN112886029B (en) | Preparation and application of bifunctional oxygen electrocatalyst with hollow carbon nanotube as carrier | |
| CN111916709B (en) | Preparation method of electrode material for water system zinc ion hybrid energy storage device | |
| CN109390162A (en) | A kind of manganese cobalt sulfide/redox graphene composite material and preparation method with excellent electrochemical performance | |
| CN105428647A (en) | Cobalt diselenide/carbon nanomaterial, preparation method therefor and application thereof | |
| CN110767462A (en) | Bimetal nickel-cobalt telluride supercapacitor electrode material and preparation method thereof | |
| CN111048325A (en) | Morphology-controllable nickel manganese sulfide/graphene composite material used as supercapacitor and preparation method thereof | |
| CN110526299B (en) | Core-shell structure Fe2O3Preparation method of @ PPy composite material and application of @ PPy composite material in supercapacitor | |
| CN105271438A (en) | Preparation method of magnesium cobaltate porous structure electrode material with double-sea urchin shape | |
| CN112614992B (en) | Nickel composite positive electrode material of water-based zinc-nickel battery and preparation method of nickel composite positive electrode material | |
| CN109473634B (en) | Method for solid-phase co-thermal synthesis of molybdenum diselenide/nitrogen-doped carbon rod | |
| CN109346672A (en) | Cobalt black and multi-walled carbon nanotube integrated electrode and preparation method thereof | |
| CN110415993B (en) | Preparation method and application of Mn-Co-S/Co-MOF nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FGA | Letters patent sealed or granted (standard patent) |