CN103474258A - Method for preparing super capacitor electrode material with foamed nickel loaded with Cu and Cu2O - Google Patents
Method for preparing super capacitor electrode material with foamed nickel loaded with Cu and Cu2O Download PDFInfo
- Publication number
- CN103474258A CN103474258A CN2013104214289A CN201310421428A CN103474258A CN 103474258 A CN103474258 A CN 103474258A CN 2013104214289 A CN2013104214289 A CN 2013104214289A CN 201310421428 A CN201310421428 A CN 201310421428A CN 103474258 A CN103474258 A CN 103474258A
- Authority
- CN
- China
- Prior art keywords
- cu2o
- foamed nickel
- electrode material
- nickel foam
- super capacitor
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 30
- 239000003990 capacitor Substances 0.000 title claims abstract description 17
- 239000007772 electrode material Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title abstract 7
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title abstract 7
- 239000010949 copper Substances 0.000 claims abstract description 49
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004202 carbamide Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000006260 foam Substances 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 abstract 2
- 238000002604 ultrasonography Methods 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 239000011149 active material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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 provides a method for preparing a super capacitor electrode material with foamed nickel loaded with Cu and Cu2O. Firstly, copper nitrate hydrate is mixed with urea, and therefore a mixed solution of copper nitrate hydrate of 0.05-0.10mol/L and urea of 0.5-1.0mol/L is prepared. Secondly, the foamed nickel undergoes oil removing with acetone in an ultrasound mode for 15min and is etched by HCl of 0.5-1.0mol/L for 3-6min, and the foamed nickel is cleaned by distilled water. Thirdly, the mixed solution obtained in the first step is transferred into a reaction kettle, and the foamed nickel leans obliquely in the reaction kettle and is reacted for 10-15h under the temperature of 90-95 DEG C. Fourthly, the reaction kettle is cooled naturally to be in the room temperature, the foamed nickel is taken out, and sediment is removed in an ultrasound mode. Fifthly, drying is performed for 10-15h under the temperature between 50 DEG C and 60 DEG C, a mixture of Cu and Cu2O is obtained, the mol ratio of Cu2O and Cu is 80-85:20-15. According to the method for preparing the super capacitor electrode material with the foamed nickel loaded with Cu and Cu2O, on one hand, the specific capacity of the active substance Cu2O is high, on the other hand, the electric conductivity of Cu is strong, and the weakness of low electrical conductivity of Cu2O is made up for.
Description
Technical field
That the present invention relates to is a kind of preparation method of electrochemical capacitor electrode material, and specifically a kind of nickel foam is carried Cu/Cu
2the preparation method of the electrode material of O.
Background technology
Ultracapacitor is a kind of energy-storage travelling wave tube that utilizes the electrochemical process storage electric charge of electrode/solution surface, also is electrochemical capacitor.But it has fast charging and discharging, and life-span length, the warm limit for width of working, advantage that the voltage Memorability is good, non-maintaining, be a kind of novel, efficient, practical energy accumulating device.
In order further to improve the energy density of ultracapacitor, developed in recent years hybrid super capacitor.Hybrid super capacitor is to utilize metal oxide and active carbon respectively as the capacitor of both positive and negative polarity electrode material, and its working mechanism is mainly electric double layer principle and pseudo capacitance principle.Electric double layer capacitance allows large electric current fast charging and discharging, and pseudo capacitance can react to realize that macro-energy storage, the large capacity of ultracapacitor and high power discharge and recharge by these two kinds of principles generations by quick reversible faraday.And both combine can produce higher operating voltage, so the energy density of mixed capacitor is much larger than double electric layer capacitor, but its charging and discharging curve has again significantly non-linear simultaneously.Due to the energy storage mechanism difference of both positive and negative polarity in the charge and discharge process of ultracapacitor, so it has the double characteristic of double electric layer capacitor and pseudo capacitance device.
Electrode material is one of key factor determined the ultracapacitor performance, so the research of electrode material also becomes the focus of ultracapacitor research.Research to electrode material mainly concentrates on the active material that height ratio capacity, high-energy-density, high power density, low ESR and cost performance are high.Cu wherein
2o is a kind of important transition metal oxide electrode material.
During electrode charge, Cu
2o is oxidized to CuO; During electrode discharge, CuO restores as Cu
2o is referring to (1) formula.
Specifically can be referring to document Zhang H X, Zhang M L.Synthesis of CuO nanocrystalline and their application aselectrode materials for capacitors.Materials Chemistry and Physics, 108 (2008) 184 – 187., and Zhang H X, Feng J, Zhang M L.Preparation of flower-like CuO by a simple chemical precipitation method and their application as electrode materials for capacitor[J] .Materials Research Bulletin, 43 (2008) 3221 – 3226.
Summary of the invention
The specific capacity that the purpose of this invention is to provide a kind of active material is high, and conductivity is high, and the nickel foam that the cycle performance is good is carried Cu/Cu
2the preparation method of the electrode material for super capacitor of O.
The object of the present invention is achieved like this:
(1), nitrate trihydrate copper is mixed with urea, be made into 0.05-0.10molL
-1nitrate trihydrate copper and 0.5-1.0molL
-1the mixed solution of urea; (2), acetone ultrasonic oil removing 15min for nickel foam, 6molL
-1hCl etching 3-6min, clean up with distilled water afterwards; (3), step (1) gained mixed solution is transferred in reactor, nickel foam leans in reactor, 90-95 ℃ of reaction 10-15h; (4), reactor room temperature when naturally cooling, take out nickel foam, ultrasonic removal deposit; (5), 50-60 ℃ of dry 10-15h obtains Cu/Cu
2the mixture of O, Cu
2the molar ratio of O and Cu is about 80-85:20-15.
The present invention prepares nickel foam with hydro-thermal reaction and displacement reaction and carries Cu/Cu
2o, then carry Cu/Cu with nickel foam
2o is electrode material, presses (1) formula and is discharged and recharged, then forming ultracapacitor with other electrode material.
Essence of the present invention is to adopt supercapacitor structures, with nickel foam, carries Cu/Cu
2o replaces reactive powder and mixes with active carbon and binding agent the way be pressed into again on nickel foam, forms the electrode of ultracapacitor.
The invention has the advantages that and utilize nickel foam to carry Cu/Cu
2o, as the electrode material of ultracapacitor, has realized Cu and Cu
2o is synthetic in the original position on nickel foam surface with certain proportion, on the one hand active material Cu
2the specific capacity of O is high, and the conductivity of Cu is strong on the other hand, has made up Cu
2the weakness that the O conductivity is low.Nickel foam is carried Cu/Cu
2o is not only used conductive agent and binding agent, and active material utilization is improved greatly, and specific capacity increases, and the cycle performance improves.
Embodiment
Below for example the present invention is described in more detail:
(1),, according to nitrate trihydrate copper 0.05-0.10molL
-1, urea 0.5-1.0molL
-1ratio nitrate trihydrate copper is mixed with urea, use magnetic stirrer 10-15min, form blue homogeneous solution.(2), the nickel foam of clip 3cm * 5cm, the ultrasonic oil removing 15min of acetone, 6molL
-1hCl etching 3-6min, clean up with distilled water afterwards.(3), above homogeneous solution is transferred in autoclave, nickel foam leans in reactor, 90-95 ℃ of reaction 10-15h.(4), reactor room temperature when naturally cooling, take out nickel foam, ultrasonic removal deposit.(5), 50-60 ℃ of dry 10-15h obtains Cu/Cu
2the mixture of O, Cu
2the molar ratio of O and Cu is about 80-85:20-15.
For effect of the present invention is described better, below with concrete application example, be illustrated.
Application example 1
Utilize nickel foam to carry Cu/Cu
2o is as positive pole, with 6molL
-1kOH as electrolyte, nylon-polypropylene fibre is as barrier film, activated carbon electrodes, as the negative pole of battery, obtains nickel foam and carries Cu/Cu
2o/ active carbon mixed capacitor.With current density 5mAcm
-2during constant current charge-discharge, the high specific capacity is 125Fg
-1, the specific discharge capacity after 500 times that circulates still keeps 98Fg
-1.
Application example 2
Utilize nickel foam to carry Cu/Cu
2o is as work electrode, with 6molL
-1kOH as electrolyte, platinum electrode is to electrode, saturated calomel electrode (SCE) is as reference electrode, with current density 5mAcm
-2constant current charge-discharge is tested its specific discharge capacity and is reached as high as 452Fg
-1, after charge and discharge cycles 500 times, the special capacity fade rate is 3.2%.
Claims (1)
1. a nickel foam is carried Cu/Cu
2the preparation method of the electrode material for super capacitor of O is characterized in that: (1), nitrate trihydrate copper is mixed with urea is made into 0.05-0.10molL
-1nitrate trihydrate copper and 0.5-1.0molL
-1the mixed solution of urea; (2), acetone ultrasonic oil removing 15min for nickel foam, 6molL
-1hCl etching 3-6min, clean up with distilled water afterwards; (3), step (1) gained mixed solution is transferred in reactor, nickel foam leans in reactor, 90-95 ℃ of reaction 10-15h; (4), reactor room temperature when naturally cooling, take out nickel foam, ultrasonic removal deposit; (5), 50-60 ℃ of dry 10-15h obtains Cu/Cu
2the mixture of O, Cu
2the molar ratio of O and Cu is about 80-85:20-15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310421428.9A CN103474258B (en) | 2013-09-16 | 2013-09-16 | A kind of nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310421428.9A CN103474258B (en) | 2013-09-16 | 2013-09-16 | A kind of nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103474258A true CN103474258A (en) | 2013-12-25 |
| CN103474258B CN103474258B (en) | 2016-04-20 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310421428.9A Expired - Fee Related CN103474258B (en) | 2013-09-16 | 2013-09-16 | A kind of nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103474258B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057478A (en) * | 2016-05-11 | 2016-10-26 | 郑州大学 | Preparation method of generating rough CuS nanosheet array on foamed nickel surface and application of rough CuS nanosheet array |
| CN108677191A (en) * | 2018-05-30 | 2018-10-19 | 大连交通大学 | A kind of nano wire skeleton three-dimensional porous foams nickel and preparation method thereof |
| CN110180552A (en) * | 2019-06-28 | 2019-08-30 | 武汉工程大学 | Copper/cuprous oxide/molybdenum dioxide electrocatalysis material and preparation method thereof, application |
| CN110952112A (en) * | 2019-12-24 | 2020-04-03 | 济南大学 | Graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and preparation method and application thereof |
| CN111564326A (en) * | 2020-06-24 | 2020-08-21 | 河北工业大学 | Cu2Preparation method of O-Cu/titanium dioxide nanotube array composite electrode |
| CN112604689A (en) * | 2020-11-25 | 2021-04-06 | 电子科技大学 | Preparation of porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition |
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|---|---|---|---|---|
| CN102315433A (en) * | 2011-09-07 | 2012-01-11 | 中国矿业大学 | Graphene loaded Cu-CuxO composite material and preparation method thereof |
| CN102629685A (en) * | 2012-04-10 | 2012-08-08 | 上海交通大学 | Preparation method of Cu2O/Cu/PPy nanowire composite lithium ion battery negative material |
| CN102849778A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Octahedron cuprous oxide crystal and preparation method thereof |
-
2013
- 2013-09-16 CN CN201310421428.9A patent/CN103474258B/en not_active Expired - Fee Related
Patent Citations (3)
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| CN102315433A (en) * | 2011-09-07 | 2012-01-11 | 中国矿业大学 | Graphene loaded Cu-CuxO composite material and preparation method thereof |
| CN102629685A (en) * | 2012-04-10 | 2012-08-08 | 上海交通大学 | Preparation method of Cu2O/Cu/PPy nanowire composite lithium ion battery negative material |
| CN102849778A (en) * | 2012-09-21 | 2013-01-02 | 中国科学院过程工程研究所 | Octahedron cuprous oxide crystal and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| BO ZHOU等: "Enhanced photocatalytic activity of flowerlike Cu2O/Cu prepared using solvent-thermal route", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
| 周波等: "花状Cu2O /Cu复合材料的光催化性能", 《高等学校化学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106057478A (en) * | 2016-05-11 | 2016-10-26 | 郑州大学 | Preparation method of generating rough CuS nanosheet array on foamed nickel surface and application of rough CuS nanosheet array |
| CN106057478B (en) * | 2016-05-11 | 2018-08-24 | 郑州大学 | In the preparation method and applications of the coarse CuS nanosheet array of nickel foam Surface Creation |
| CN108677191A (en) * | 2018-05-30 | 2018-10-19 | 大连交通大学 | A kind of nano wire skeleton three-dimensional porous foams nickel and preparation method thereof |
| CN110180552A (en) * | 2019-06-28 | 2019-08-30 | 武汉工程大学 | Copper/cuprous oxide/molybdenum dioxide electrocatalysis material and preparation method thereof, application |
| CN110180552B (en) * | 2019-06-28 | 2022-05-10 | 武汉工程大学 | Copper/cuprous oxide/molybdenum dioxide electrocatalytic material and preparation method and application thereof |
| CN110952112A (en) * | 2019-12-24 | 2020-04-03 | 济南大学 | Graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and preparation method and application thereof |
| CN110952112B (en) * | 2019-12-24 | 2021-07-27 | 济南大学 | Graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and preparation method and application thereof |
| CN111564326A (en) * | 2020-06-24 | 2020-08-21 | 河北工业大学 | Cu2Preparation method of O-Cu/titanium dioxide nanotube array composite electrode |
| CN111564326B (en) * | 2020-06-24 | 2021-09-28 | 河北工业大学 | Cu2Preparation method of O-Cu/titanium dioxide nanotube array composite electrode |
| CN112604689A (en) * | 2020-11-25 | 2021-04-06 | 电子科技大学 | Preparation of porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition |
| CN112604689B (en) * | 2020-11-25 | 2022-03-15 | 电子科技大学 | Preparation of porous copper oxide skeleton catalyst for catalyzing formaldehyde decomposition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103474258B (en) | 2016-04-20 |
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Granted publication date: 20160420 |