CN103578784A - Nanometer copper oxide composite material and preparation method thereof and super-capacitor electrode and super-capacitor - Google Patents

Nanometer copper oxide composite material and preparation method thereof and super-capacitor electrode and super-capacitor Download PDF

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Publication number
CN103578784A
CN103578784A CN201310485716.0A CN201310485716A CN103578784A CN 103578784 A CN103578784 A CN 103578784A CN 201310485716 A CN201310485716 A CN 201310485716A CN 103578784 A CN103578784 A CN 103578784A
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carbon
composite material
preparation
copper
nano oxidized
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CN103578784B (en
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张小俊
南红红
马文勤
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Anhui Normal University
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Anhui Normal 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

Abstract

The invention relates to a nanometer copper oxide composite material, a preparation method thereof, a super-capacitor electrode and a super-capacitor. The hydrothermal method is used for directly enabling a copper oxide nanometer structure to grow on the surface of foamy copper. The obtained three-dimensional net-like nanometer copper oxide composite material can be applied to construction of the super-capacitor electrode, so that the specific capacity of the super-capacitor is improved, and the cycle life is prolonged.

Description

A kind of nano oxidized carbon/carbon-copper composite material and preparation method thereof, electrode of super capacitor and ultracapacitor
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of nano oxidized carbon/carbon-copper composite material and preparation method thereof, electrode of super capacitor and ultracapacitor.
Background technology
Along with the development that science and technology is advanced by leaps and bounds, as the traditional electrode of ultracapacitor, can not be satisfied with gradually reality needs.Capacitor electrode material has: material with carbon element class electrode material, conducting polymer class electrode material, metal oxide composite electrode material.Because various single electrode materials have shortcoming separately, as poorly conductive, the little grade of specific area and be difficult to the application requirements that reaches higher.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of nano oxidized carbon/carbon-copper composite material and preparation method thereof, electrode of super capacitor and ultracapacitor, the present invention uses hydro thermal method directly to make cupric oxide nano structure length on the surface of foam copper, the nano oxidized carbon/carbon-copper composite material of three-dimensional network shape obtaining, the structure that can be used for electrode of super capacitor, realize the raising of ultracapacitor specific capacity, the prolongation of cycle life.
The technical solution used in the present invention is:
A carbon/carbon-copper composite material, forms by foam copper and at its epontic nano cupric oxide, and the nano cupric oxide of its growth is membranaceous and is laid in foam copper substrate.
A preparation method for nano oxidized carbon/carbon-copper composite material, step comprises:
A, foam copper is cleaned up; Cleaning method, for foam copper is put into acetone, ethanol, watery hydrochloric acid, water successively, carries out Ultrasonic Cleaning, and the ultrasonic cleaning time is respectively 10-15min, described watery hydrochloric acid concentration >=2mol/L;
B, ammonia spirit is added in reactor, then foam copper is immersed in ammonia spirit to closed reactor, at 80-120 ℃, react 3-5h, be cooled to room temperature, take out reacted foam copper and cleaned up, drying at room temperature, makes nano oxidized carbon/carbon-copper composite material; Described ammonia spirit concentration is 0.005-0.1mol/L, and described cleaning is cleaned water and absolute ethyl alcohol.
, use nano oxidized carbon/carbon-copper composite material preparation.
, use the electrode preparation that comprises nano oxidized carbon/carbon-copper composite material.
Nano cupric oxide composite material of the present invention under alkaline environment, adopts water to do reaction dissolvent based on foam copper, and hyperbaric heating, can be prepared at the membranaceous nano cupric oxide in foam copper Surface Creation 3D structure.
Preparation method of the present invention compared with prior art, has reappearance high, easy and simple to handle, consumes energy low, and synthetic cost is low, and product purity is high, good dispersion, good crystalline and can control, and is suitable for industrial extensive preparation; Prepared nano oxidized carbon/carbon-copper composite material has larger specific area, capacity is large, decay little, as super capacitor material, can make capacitor have high power density, long charge and discharge circulation life, short time that discharges and recharges, special power density and the energy density of appropriateness, long storage life, wide working range.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the nano oxidized carbon/carbon-copper composite material of embodiment 1 preparation.
Fig. 2 is the electron scanning micrograph (SEM) of the nano oxidized carbon/carbon-copper composite material of embodiment 1 preparation.
Fig. 3 is the nano oxidized carbon/carbon-copper composite material of embodiment 1 preparation carries out Electrochemical Detection in alkaline solution cyclic voltammogram (CV) as electrode of super capacitor.
In figure:
1 is that electrode is swept speed for 5mV s in the sodium hydroxide solution of 0.1M -1cyclic voltammetry curve.
2 is that electrode is swept speed for 10mV s in the sodium hydroxide solution of 0.1M -1cyclic voltammetry curve.
3 is that electrode is swept speed for 20mV s in the sodium hydroxide solution of 0.1M -1cyclic voltammetry curve.
4 is that electrode is swept speed for 50mV s in the sodium hydroxide solution of 0.1M -1cyclic voltammetry curve.
5 is that electrode is swept speed for 100mV s in the sodium hydroxide solution of 0.1M -1cyclic voltammetry curve.
Fig. 4 is that the nano oxidized carbon/carbon-copper composite material of embodiment 1 preparation carries out the electrograph that charges and discharge of Electrochemical Detection in alkaline solution kind as electrode of super capacitor.
In figure:
1 is electrode 1A g in the sodium hydroxide solution of 0.1M -1charging and discharging curve.
2 is electrode 2A g in the sodium hydroxide solution of 0.1M -1charging and discharging curve.
3 is electrode 5A g in the sodium hydroxide solution of 0.1M -1charging and discharging curve.
4 is electrode 10A g in the sodium hydroxide solution of 0.1M -1charging and discharging curve.
5 is electrode 20A g in the sodium hydroxide solution of 0.1M -1charging and discharging curve.
Fig. 5 is the electron scanning micrograph (SEM) of the nano oxidized carbon/carbon-copper composite material of embodiment 2 preparations.
Fig. 6 is the electron scanning micrograph (SEM) of the nano oxidized carbon/carbon-copper composite material of embodiment 3 preparations.
Fig. 7 is the electron scanning micrograph (SEM) of the nano oxidized carbon/carbon-copper composite material of embodiment 4 preparations.
Specific implementation method
Embodiment 1
A carbon/carbon-copper composite material, forms by foam copper and at its epontic nano cupric oxide.
A preparation method for nano oxidized carbon/carbon-copper composite material, step comprises:
A, foam copper is put into acetone, ethanol, watery hydrochloric acid, water successively, carry out Ultrasonic Cleaning; In acetone, ethanol, watery hydrochloric acid, water the ultrasonic cleaning time be respectively 10,15,10,10min, described watery hydrochloric acid concentration is 3mol/L;
B, the ammonia spirit of 20mL0.05mol/L being added in reactor, is then 2.5mm by cross-sectional area 2, length is that 4cm foam copper immerses in ammonia spirit, tightens reaction kettle cover, at 100 ℃, react 4h, be cooled to room temperature, take out reacted foam copper and clean up with distilled water and absolute ethyl alcohol, drying at room temperature, makes the nano oxidized carbon/carbon-copper composite material of three-dimensional network shape.
, use nano oxidized carbon/carbon-copper composite material preparation.
, use the electrode preparation that comprises nano oxidized carbon/carbon-copper composite material.
As shown in Figure 2, cupric oxide is the membranaceous surface that is laid in foam copper to the pattern of made nano oxidized carbon/carbon-copper composite material.
Get 10mL0.1M NaOH solution and put into electrolysis tank as electrolyte solution, using the nano oxidized carbon/carbon-copper composite material of preparation in embodiment 1 as work electrode, sweeping speed for 5mV s -1time survey cyclic voltammetry curve (in Fig. 3, curve 1), then sweeping speed for 10mV s -1time survey cyclic voltammetry curve (in Fig. 3, curve 2), the like obtain sweeping speed for 20mV s -1(in Fig. 3, curve 3), 50mV s -1(in Fig. 3, curve 4), 100mV s -1(in Fig. 3, curve 5), can find out from the CV figure obtaining, fast increase voltage is linear along with sweeping.
Get 10ml0.1M NaOH solution and put into electrolysis tank as electrolyte solution, using the nano oxidized carbon/carbon-copper composite material of preparation in embodiment 1 as work electrode, at 1A g -1time obtain charging and discharging curve (in Fig. 4, curve 1), at 2A g -1time obtain charging and discharging curve (in Fig. 4, curve 2), at 5A g -1time obtain charging and discharging curve (in Fig. 4, curve 3), at 10A g -1time obtain charging and discharging curve (in Fig. 4, curve 4), at 20A g -1time obtain charging and discharging curve (in Fig. 4, curve 5), from charging and discharging curve, can show that foam copper nano composite material is compared other material capacity as electrode very large, by calculating electrode capacity, be 671F g -1.
Embodiment 2
A carbon/carbon-copper composite material, forms by foam copper and at its epontic nano cupric oxide.
A preparation method for nano oxidized carbon/carbon-copper composite material, step comprises:
A, foam copper is put into acetone, ethanol, watery hydrochloric acid, water successively, carry out Ultrasonic Cleaning; In acetone, ethanol, watery hydrochloric acid, water the ultrasonic cleaning time be respectively 15,15,15,15min, described watery hydrochloric acid concentration is 3mol/L;
B, the ammonia spirit of 20mL0.005mol/L being added in reactor, is then 2.5mm by cross-sectional area 2, length is that 4cm foam copper immerses in ammonia spirit, tightens reaction kettle cover, at 120 ℃, react 5h, be cooled to room temperature, take out reacted foam copper and clean up with distilled water and absolute ethyl alcohol, drying at room temperature, makes the nano oxidized carbon/carbon-copper composite material of three-dimensional network shape.
, use nano oxidized carbon/carbon-copper composite material preparation.
, use the electrode preparation that comprises nano oxidized carbon/carbon-copper composite material.
Embodiment 3
A carbon/carbon-copper composite material, forms by foam copper and at its epontic nano cupric oxide.
A preparation method for nano oxidized carbon/carbon-copper composite material, step comprises:
A, foam copper is put into acetone, ethanol, watery hydrochloric acid, water successively, carry out Ultrasonic Cleaning; In acetone, ethanol, watery hydrochloric acid, water the ultrasonic cleaning time be respectively 12,10,12,10min, described watery hydrochloric acid concentration is 2mol/L;
B, the ammonia spirit of 20mL0.1mol/L being added in reactor, is then 2.5mm by cross-sectional area 2, length is that 4cm foam copper immerses in ammonia spirit, tightens reaction kettle cover, at 80 ℃, react 5h, be cooled to room temperature, take out reacted foam copper and clean up with distilled water and absolute ethyl alcohol, drying at room temperature, makes the nano oxidized carbon/carbon-copper composite material of three-dimensional network shape.
, use nano oxidized carbon/carbon-copper composite material preparation.
, use the electrode preparation that comprises nano oxidized carbon/carbon-copper composite material.
Embodiment 4
A carbon/carbon-copper composite material, forms by foam copper and at its epontic nano cupric oxide.
A preparation method for nano oxidized carbon/carbon-copper composite material, step comprises:
A, foam copper is put into acetone, ethanol, watery hydrochloric acid, water successively, carry out Ultrasonic Cleaning; In acetone, ethanol, watery hydrochloric acid, water the ultrasonic cleaning time be respectively 12,12,12,12min, described watery hydrochloric acid concentration is 5mol/L;
B, the ammonia spirit of 20mL0.1mol/L being added in reactor, is then 2.5mm by cross-sectional area 2, length is that 4cm foam copper immerses in ammonia spirit, tightens reaction kettle cover, at 110 ℃, react 3h, be cooled to room temperature, take out reacted foam copper and clean up with distilled water and absolute ethyl alcohol, drying at room temperature, makes the nano oxidized carbon/carbon-copper composite material of three-dimensional network shape.
, use nano oxidized carbon/carbon-copper composite material preparation.
, use the electrode preparation that comprises nano oxidized carbon/carbon-copper composite material.

Claims (7)

1. a nano oxidized carbon/carbon-copper composite material, forms by foam copper and at its epontic nano cupric oxide, and nano cupric oxide is membranaceous and is laid in foam copper substrate.
2. a preparation method for nano oxidized carbon/carbon-copper composite material, step comprises:
A, foam copper is cleaned up;
B, ammonia spirit is added in reactor, then foam copper is immersed in ammonia spirit to closed reactor, at 80-120 ℃, react 3-5h, be cooled to room temperature, take out reacted foam copper and cleaned up, drying at room temperature, makes nano oxidized carbon/carbon-copper composite material; Described ammonia spirit concentration is 0.005-0.1mol/L.
3. preparation method as claimed in claim 2, is characterized in that: in described step a, cleaning method, for foam copper is put into acetone, ethanol, watery hydrochloric acid, water successively, carries out Ultrasonic Cleaning.
4. preparation method as claimed in claim 3, is characterized in that: in described step a, in acetone, ethanol, watery hydrochloric acid, water, the ultrasonic cleaning time is respectively 10-15min, described watery hydrochloric acid concentration >=2mol/L.
5. preparation method as claimed in claim 2, is characterized in that: described step b cleans water and absolute ethyl alcohol are cleaned.
6. an electrode of super capacitor, is used nano oxidized carbon/carbon-copper composite material preparation.
7. a super capacitor, is used the electrode preparation that comprises nano oxidized carbon/carbon-copper composite material.
CN201310485716.0A 2013-10-16 2013-10-16 Nanometer copper oxide composite material and preparation method thereof and super-capacitor electrode and super-capacitor Expired - Fee Related CN103578784B (en)

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CN107871627A (en) * 2016-09-28 2018-04-03 南京大学 Foam copper supports high capacitance flexible electrode material of CuO nanometer sheet and preparation method thereof
CN108823588A (en) * 2018-06-05 2018-11-16 青岛科技大学 A kind of Cu of Ag modification2O nanobelt/foam copper combination electrode and preparation method thereof
CN110970596A (en) * 2018-09-29 2020-04-07 清华大学 Lithium ion battery cathode, preparation method thereof and lithium ion battery

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107871627A (en) * 2016-09-28 2018-04-03 南京大学 Foam copper supports high capacitance flexible electrode material of CuO nanometer sheet and preparation method thereof
CN108823588A (en) * 2018-06-05 2018-11-16 青岛科技大学 A kind of Cu of Ag modification2O nanobelt/foam copper combination electrode and preparation method thereof
CN110970596A (en) * 2018-09-29 2020-04-07 清华大学 Lithium ion battery cathode, preparation method thereof and lithium ion battery
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