CN103474258B - A kind of nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O - Google Patents

A kind of nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O Download PDF

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CN103474258B
CN103474258B CN201310421428.9A CN201310421428A CN103474258B CN 103474258 B CN103474258 B CN 103474258B CN 201310421428 A CN201310421428 A CN 201310421428A CN 103474258 B CN103474258 B CN 103474258B
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nickel foam
electrode material
urea
super capacitor
mixed solution
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CN103474258A (en
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王贵领
黄纪春
潘越
曹殿学
杨赛男
刘彤
刘新伟
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Harbin Engineering University
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Harbin Engineering University
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    • 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

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  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention is to provide a kind of nickel foam and carry Cu/Cu 2the preparation method of the electrode material for super capacitor of O.(1), by nitrate trihydrate copper mix with urea, be made into 0.05-0.10molL -1nitrate trihydrate copper and 0.5-1.0molL -1the mixed solution of urea; (2), nickel foam acetone ultrasonic oil removing 15min, 6molL -1hCl etches 3-6min, cleans up afterwards with distilled water; (3), be transferred in reactor by step (1) gained mixed solution, nickel foam leans in a kettle., 90-95 DEG C of reaction 10-15h; (4), reactor room temperature when naturally cooling, take out nickel foam, ultrasonic removal deposit; (5), 50-60 DEG C 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.One aspect of the present invention active material Cu 2the specific capacity of O is high, and the conductivity of Cu is strong on the other hand, compensate for Cu 2the weakness that O conductivity is low.

Description

A kind of nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O
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 carries Cu/Cu 2the preparation method of the electrode material of O.
Background technology
Ultracapacitor is a kind of energy-storage travelling wave tube utilizing the electrochemical process of electrode/solution surface to store electric charge, is also electrochemical capacitor.It has can fast charging and discharging, and life-span length, the warm limit for width that works, advantage that voltage Memorability is good, non-maintaining, be a kind of novel, efficient, practical energy accumulating device.
In order to improve the energy density of ultracapacitor further, have developed hybrid super capacitor in recent years.Hybrid super capacitor utilizes metal oxide and active carbon respectively as the capacitor of both positive and negative polarity electrode material, and its working mechanism is electric double layer principle and pseudo capacitance principle mainly.Electric double layer capacitance allows big current fast charging and discharging, and pseudo capacitance realizes macro-energy by faraday's reaction of Rapid reversible and stores, and the Large Copacity of ultracapacitor and high power discharge and recharge are produced by these two kinds of principles.And both combine can produce higher operating voltage, and therefore 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.Because in the charge and discharge process of ultracapacitor, the energy storage mechnism of both positive and negative polarity is different, therefore it has the double characteristic of double electric layer capacitor and Faradic pseudo-capacitor.
Electrode material is one of key factor determining ultracapacitor performance, so the research of electrode material also becomes the focus of ultracapacitor research.The research of electrode material is mainly concentrated on the high active material of height ratio capacity, high-energy-density, high power density, low ESR and cost performance.Wherein Cu 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 see (1) formula.
Specifically can see document ZhangHX, ZhangML.SynthesisofCuOnanocrystallineandtheirapplication aselectrodematerialsforcapacitors.MaterialsChemistryandP hysics, 108 (2008) 184 – 187, and ZhangHX, FengJ, ZhangML.Preparationofflower-likeCuObyasimplechemicalprec ipitationmethodandtheirapplicationaselectrodematerialsfo rcapacitor [J] .MaterialsResearchBulletin, 43 (2008) 3221 – 3226.
Summary of the invention
The specific capacity that the object of this invention is to provide a kind of active material is high, and conductivity is high, and the nickel foam that cycle performance is good carries 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), by nitrate trihydrate copper mix with urea, be made into 0.05-0.10molL -1nitrate trihydrate copper and 0.5-1.0molL -1the mixed solution of urea; (2), nickel foam acetone ultrasonic oil removing 15min, 6molL -1hCl etches 3-6min, cleans up afterwards with distilled water; (3), be transferred in reactor by step (1) gained mixed solution, nickel foam leans in a kettle., 90-95 DEG C of reaction 10-15h; (4), reactor room temperature when naturally cooling, take out nickel foam, ultrasonic removal deposit; (5), 50-60 DEG C 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 carries Cu/Cu 2o, then carry Cu/Cu with nickel foam 2o is electrode material, presses (1) formula and carries out discharge and recharge, then forms ultracapacitor with other electrode material.
Essence of the present invention adopts supercapacitor structures, carries Cu/Cu with nickel foam 2o replaces reactive powder and mixes with active carbon and binding agent the way be pressed into again in 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, achieves Cu and Cu 2o with the fabricated in situ of certain proportion on nickel foam surface, 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, compensate for Cu 2the weakness that O conductivity is low.Nickel foam carries Cu/Cu 2o does not only use conductive agent and binding agent, and active material utilization is improved greatly, and specific capacity increases, and cycle performance improves.
Embodiment
Illustrate below and the present invention be 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, acetone ultrasonic oil removing 15min, 6molL -1hCl etches 3-6min, cleans up afterwards with distilled water.(3), be transferred in autoclave by above homogeneous solution, nickel foam leans in a kettle., 90-95 DEG C of reaction 10-15h.(4), reactor room temperature when naturally cooling, take out nickel foam, ultrasonic removal deposit.(5), 50-60 DEG C 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.
In order to effect of the present invention is described better, be illustrated with embody rule example below.
Application example 1
Nickel foam is utilized to carry Cu/Cu 2o as positive pole, with 6molL -1kOH as electrolyte, nylon-polypropylene fibre is as barrier film, and 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, high specific capacity is 125Fg -1, the specific discharge capacity after 500 times that circulates still keeps 98Fg -1.
Application example 2
Nickel foam is utilized to carry Cu/Cu 2o as work electrode, with 6molL -1kOH as electrolyte, platinum electrode is to electrode, saturated calomel electrode (SCE) 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, special capacity fade rate is 3.2%.

Claims (1)

1. a nickel foam carries Cu/Cu 2the preparation method of the electrode material for super capacitor of O, is characterized in that: (1), mixed with urea by nitrate trihydrate copper, is made into 0.05-0.10molL -1nitrate trihydrate copper and 0.5-1.0molL -1the mixed solution of urea; (2), nickel foam acetone ultrasonic oil removing 15min, 6molL -1hCl etches 3-6min, cleans up afterwards with distilled water; (3), be transferred in reactor by step (1) gained mixed solution, nickel foam leans in a kettle., 90-95 DEG C of reaction 10-15h; (4), reactor room temperature when naturally cooling, take out nickel foam, ultrasonic removal deposit; (5), 50-60 DEG C of dry 10-15h obtains Cu/Cu 2the mixture of O, Cu 2the molar ratio of O and Cu is 80-85:20-15.
CN201310421428.9A 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 Active CN103474258B (en)

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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
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
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
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
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

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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
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