CN103151182B - A kind of nano nickel oxide electrode material and application thereof - Google Patents
A kind of nano nickel oxide electrode material and application thereof Download PDFInfo
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- CN103151182B CN103151182B CN201310049616.3A CN201310049616A CN103151182B CN 103151182 B CN103151182 B CN 103151182B CN 201310049616 A CN201310049616 A CN 201310049616A CN 103151182 B CN103151182 B CN 103151182B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003990 capacitor Substances 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 7
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 7
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 3
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000004087 circulation Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910001453 nickel ion Inorganic materials 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of nano nickel oxide electrode material, take lignosulfonates as template, under solution state, introduce nickel ion, make its precipitate and separate after recombination reaction, then remove masterplate, finally obtain nano nickel oxide electrode material.The invention has the beneficial effects as follows: template agent environmental protection needed for the method is cheap and be easy to get, preparation method is simple.The nano oxidized nickel material made has high-specific surface area, good circulation and large current density electrical stability, and the advantages such as high specific capacitance, are suitable as the electrode material of ultracapacitor very much.
Description
Technical field
The invention belongs to electrochemistry and new energy materials field, in particular, provide a kind of preparation method of nano nickel oxide electrode material and the application as electrode material for super capacitor thereof.
Background technology
In recent years, along with the development of electric automobile and various electronic equipment, electrochemical capacitor becomes study hotspot gradually. compared with traditional capacitor, electrochemical capacitor energy density is higher, operating temperature range is wider. and meanwhile, it has again the incomparable high power density of traditional chemical power supply, long circulation life and superior pulse charge-discharge performance.
Well-known unformed ruthenium oxide hydration is the most promising electrode material of high power high-energy density super capacitor, but expensive scarcity of resources, electrolyte pollution environment used, greatly limit its business development.The oxide electrode materials such as nickel oxide have the function similar to ruthenium oxide hydration, and low price, very by the concern of researcher.Although explored the method for multiple synthesis of nano nickel oxide in recent years, still there is following problem has needed to solve: (1) complicated process of preparation, long flow path; (2) with a large amount of organic solvent of the many employings of nano NiO solid that sol-gel process obtains, solvent evaporates in gel process is formed harmful, not environmentally.(3), in template synthesis nano NiO process, template cost is higher, is unfavorable for large-scale production.
In addition, large quantity research shows, the factors such as the chemical property of NiO and pattern, specific area, pore structure are closely related.The chemical property that the NiO material usually with the flourishing pore structure of high-ratio surface sum shows is more excellent.
Therefore, how to make NiO preparation process technique simple, flow process shortens, the raw material environmental sound of employing, and cost is low etc. seems most important.And seek a kind of new preparation method, obtained NiO material has that high-specific surface area, high porosity, long service life, good cycling stability, ratio capacitance are high, electrochemical performance is the important key realizing modern production.
Summary of the invention
The object of the present invention is to provide a kind of nano nickel oxide electrode material that can be used for ultracapacitor and preparation method thereof.
The technical solution used in the present invention is:
A kind of nano nickel oxide electrode material, described nano nickel oxide electrode material prepares by the following method: by lignosulfonates and nickel source soluble in water, add alkaline matter and obtain reactant liquor, under being heated to 70-95 DEG C of (preferably 80 ~ 90 DEG C) temperature, react 2-3 hour, generate precipitation, by centrifugal for reaction mixture rear filtration, Washing of Filter Cake, oven dry, then in 300-600 DEG C of temperature lower calcination 3 ~ 5 hours, to remove template,, obtained described nano nickel oxide electrode material; Described nickel source is one or more the mixing in nickel nitrate, nickelous sulfate, nickel chloride, preferably sulfuric acid nickel or nickel nitrate; The mass ratio of described nickel source, lignosulfonates is 1:0.6 ~ 1, and the quality amount ratio of described alkaline matter and water is 20 ~ 40:100.
Described lignosulfonates are one or both in sodium lignin sulfonate, calcium lignosulfonate, preferred sodium lignin sulfonate.
Described alkaline matter is preferably one or more the mixing in the ammoniacal liquor of mass percentage concentration 25%-28%, triethanolamine, triethylamine, potassium hydroxide, hexamethylenetetramine, is preferably hexamethylenetetramine or triethylamine.
Described nickel source is preferably nickel nitrate or nickelous sulfate.
The volumetric usage of described water counts 20 ~ 50mL/g with the quality in nickel source usually, preferably 20 ~ 40mL/g.
The temperature of described calcining is preferably 350 ~ 450 DEG C.
Described Washing of Filter Cake, oven dry, usually with distilled water washing, dry 12h-48h at 80 DEG C of temperature.
Nano nickel oxide electrode material provided by the invention can be applied as electrode material for super capacitor.The method preparing electrode of super capacitor can adopt and well known to a person skilled in the art various method.Nano nickel oxide electrode material make electrode last as need milled processed.
Beneficial effect of the present invention is: nano oxidized method for preparing nickel is simple, and lignosulfonates are easy to get as template cheaper starting materials, do not have high pollution additives to produce.And the nano oxidized nickel material of preparation has high-specific surface area, and (Fig. 2, specific area reaches 238m
2g
-1), good circulation (Fig. 3) and high current charge-discharge (Fig. 5) stability, the advantages such as high specific capacitance (Fig. 4), are suitable as the electrode material of ultracapacitor very much.The present invention utilizes the biological template lignin of environmental protection cheapness to prepare New Type of Mesoporous nickel oxide, has the advantages such as high-specific surface area, high specific capacitance, low cost, has a extensive future.
Accompanying drawing explanation
The TEM figure of the nano nickel oxide electrode material that Fig. 1 embodiment 1 is obtained.
The desorption absorption figure of the nitrogen of the nano nickel oxide electrode material that Fig. 2 embodiment 1 is obtained, wherein the little figure in the upper left corner is graph of pore diameter distribution, and average pore size is between 5-20nm as can be seen from Figure.
The cyclic voltammetry curve of the nano nickel oxide electrode material that Fig. 3 embodiment 1 is obtained, in Fig. 3, curve a, b, c be respectively circulation 10 times, 500 times, 1000 times time cyclic voltammetry curve.
The nano nickel oxide electrode material ratio capacitance relative cycle frequency curve figure that Fig. 4 embodiment 1 and embodiment 2 obtain, in Fig. 4, curve N a-NiO represents the obtained nano nickel oxide electrode material of embodiment 1, and curve C a-NiO represents the obtained nano nickel oxide electrode material of embodiment 2;
Fig. 5 is the constant current charge-discharge figure of the nano nickel oxide electrode material that embodiment 1 obtains
Embodiment
Below in conjunction with specific embodiment, the present invention is conducted further description, but protection scope of the present invention is not limited thereto.Embodiment 1
Sample preparation: first 3g sodium lignin sulfonate and 3g nickelous sulfate are dissolved in 100ml deionized water, be uniformly mixed completely, then add 30g hexamethylenetetramine, heating is stirred to 80 DEG C, reacts 3 hours, produces tan precipitate.Centrifugal rear filtration, filter cake distilled water washs, then puts into vacuum drying chamber 80 DEG C of temperature oven dry 12h, obtains Tan solid.Tan solid is sent into Muffle furnace, at 350 DEG C, under air atmosphere, calcines 3 hours, obtained nano nickel oxide electrode material 1g after cooling.The TEM figure of products therefrom as shown in Figure 1.Record through BET specific surface area method of testing, the specific area of material is 238m
2g
-1, average pore size is distributed between 5-20nm, as shown in Figure 2.
Electrode fabrication: obtained nano-nickel oxide is ground to form powder, mix with the ratio of conductive agent acetylene black, polytetrafluoroethylene PTFE (binding agent) 8:1:1 in mass ratio, be coated in equably in the nickel foam of precise, dry post-drying, at 10MP tableting under pressure, makes work electrode, reference electrode is made with Ag/AgCl electrode, platinized platinum is used as auxiliary electrode, and the KOH solution of 6mol/L is that electrolyte forms three-electrode system, is used for testing chemical property.
As shown in Figure 3, setting parameter is cyclic voltammetry curve: initial potential 0V, and stop current potential 0.7V, sweep speed is 0.02V/s.In Fig. 3, curve a, b, c are circulation 10 times respectively, 500 times and 1000 times time cyclic voltammetry curve.As can be seen from the figure curvilinear motion is little, and good cycling stability is described.
According to the cyclic voltammetry curve that cyclic voltammetry obtains, by formula
the curve of the ratio capacitance relative cycle number of times calculated, as shown in Na-NiO curve in Fig. 4.As can be seen from the figure material is through 1000 circulations, and ratio capacitance is from 255F/g to 201F/g, and ratio capacitance decay is little.
Carry out constant current charge-discharge experiment, charging and discharging currents is respectively 1A/g, 2A/g, 4A/g and 10A/g, and voltage range is 0-0.7V, discharge voltage with discharge time change curve as shown in Figure 5, according to formula C
s=I Δ t/m Δ V calculates ratio capacitance, and can obtain when the curent change from 1A/g to 10A/g, ratio capacitance becomes 201F/g from 231F/g, and ratio capacitance conservation rate is 87%.Illustrative material is under high current charge-discharge, and have reasonable stability, capacitance fade is little.
Embodiment 2
Other operations and reaction condition are with embodiment 1, difference is that sodium lignin sulfonate 3g calcium lignosulfonate wherein replaces, hexamethylenetetramine 40g triethylamine replaces, and obtained nano nickel oxide electrode material carries out performance test according to the method for embodiment 1.Record through BET, the specific area of material is 203m
2g
-1, average pore size is distributed between 5-20nm.In cyclic voltammetry, the curve of ratio capacitance relative cycle number of times is as shown in Ca-NiO curve in Fig. 4.
Embodiment 3
Other operations are with reaction condition with embodiment 1, and difference is that nickelous sulfate 3g nickel nitrate wherein replaces, and obtained nano nickel oxide electrode material, carries out performance test according to the method for embodiment 1.
In constant current charge-discharge experiment, material is when the curent change from 1A/g to 10A/g, and ratio capacitance becomes 247F/g from 275F/g, and ratio capacitance conservation rate is 90%.
Embodiment 4
Other operations are with reaction condition with embodiment 2, and difference is that reaction temperature wherein becomes 90 DEG C from 80 DEG C, and the calcining heat of Muffle furnace becomes 450 DEG C from 350 DEG C, and obtained nano nickel oxide electrode material, carries out performance test according to the method for embodiment 1.
In constant current charge-discharge experiment, material is when the curent change from 1A/g to 10A/g, and ratio capacitance becomes 157F/g from 181F/g, and ratio capacitance conservation rate is 87%.
Embodiment 5
Other operations are with reaction condition with embodiment 1, and difference is 3g nickelous sulfate to become 5g nickelous sulfate, and obtained nano nickel oxide electrode material, carries out performance test according to the method for embodiment 1.
In constant current charge-discharge experiment, material is when the curent change from 1A/g to 10A/g, and ratio capacitance becomes 254F/g from 281F/g, and ratio capacitance conservation rate is 90%.
Claims (4)
1. the nano nickel oxide electrode material as electrode material for super capacitor, it is characterized in that described nano nickel oxide electrode material prepares by the following method: by lignosulfonates and nickel source soluble in water, add alkaline matter and obtain reactant liquor, 2-3 hour is reacted under being heated to 70-95 DEG C of temperature, generate precipitation, by centrifugal for reaction mixture rear filtration, Washing of Filter Cake, oven dry, again in 300-600 DEG C of temperature lower calcination 3 ~ 5 hours, obtained described nano nickel oxide electrode material; Described nickel source is one or more the mixing in nickel nitrate, nickelous sulfate, nickel chloride; The mass ratio of described nickel source, lignosulfonates is 1:0.6 ~ 1, and the quality amount ratio of described alkaline matter and water is 20 ~ 40:100; Described lignosulfonates are one or both in sodium lignin sulfonate, calcium lignosulfonate.
2. nano nickel oxide electrode material as claimed in claim 1, is characterized in that described alkaline matter is one or more the mixing in the ammoniacal liquor of mass percentage concentration 25 ~ 28%, triethanolamine, triethylamine, potassium hydroxide, hexamethylenetetramine.
3. nano nickel oxide electrode material as claimed in claim 2, is characterized in that described alkaline matter is hexamethylenetetramine or triethylamine.
4. nano nickel oxide electrode material as claimed in claim 1, is characterized in that the volumetric usage of described water counts 20 ~ 50mL/g with the quality in nickel source.
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| CN103956469A (en) * | 2014-04-28 | 2014-07-30 | 云南大学 | Hollow nanometer pipe-shaped NiO@C compound material and preparation method thereof |
| CN109148829A (en) * | 2018-08-06 | 2019-01-04 | 浙江工业大学 | A kind of biomass derived Nano Carbon nickel oxide electrode and its application |
| CN108975307A (en) * | 2018-08-06 | 2018-12-11 | 浙江工业大学 | A kind of preparation method being classified mesoporous carbon nano composite oxides nickel material |
| CN109166735A (en) * | 2018-08-06 | 2019-01-08 | 浙江工业大学 | A kind of lignin is the preparation method of the combined oxidation nickel capacitor of carbon source |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609007A (en) * | 2004-10-21 | 2005-04-27 | 上海交通大学 | Process of preparing porous nickel oxide with plant structure |
| CN102385998A (en) * | 2011-12-08 | 2012-03-21 | 南开大学 | NiO electrode material with high specific capacitance and preparation method thereof |
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| KR100649092B1 (en) * | 2005-11-02 | 2006-11-27 | 한국과학기술연구원 | Metal oxide supercapacitor having metal oxide electrode coated onto the titanium dioxide ultrafine and its fabrication method |
| CN102887550B (en) * | 2012-10-09 | 2014-07-16 | 四川大学 | Method for producing mesoporous nickel oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609007A (en) * | 2004-10-21 | 2005-04-27 | 上海交通大学 | Process of preparing porous nickel oxide with plant structure |
| CN102385998A (en) * | 2011-12-08 | 2012-03-21 | 南开大学 | NiO electrode material with high specific capacitance and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 以木质素磺酸钠为结构导向剂直接沉淀法制备纳米氧化锌的研究;郭元茹等;《黑龙江大学自然科学学报》;20120630;第29卷(第3期);第360页2.2节 * |
| 胶质碳球为模板制备NiO空心球;武拥建等;《无机化学学报》;20111230;第27卷(第12期);第2248页1.3节 * |
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