CN108172407A - A kind of combination electrode, preparation method and application - Google Patents

A kind of combination electrode, preparation method and application Download PDF

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CN108172407A
CN108172407A CN201711429800.5A CN201711429800A CN108172407A CN 108172407 A CN108172407 A CN 108172407A CN 201711429800 A CN201711429800 A CN 201711429800A CN 108172407 A CN108172407 A CN 108172407A
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electrode
carbon
combination electrode
preparation
electroplated
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CN108172407B (en
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曾玮
马悦
卫宁
姜浩
梁栋
徐超
黄林生
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Anhui University
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Anhui University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/36Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/46Metal oxides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

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  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

The present invention discloses a kind of combination electrode, belongs to electronic material and devices field, including substrate, the electroplating surface of the substrate has carbon-coating, and the electroplating surface of the carbon-coating has transition metal oxide layer;The combination electrode is in three-dimensional porous pleated structure, and the quality specific capacitance maximum of combination electrode is up to 1783Fg‑1;The preparation method of the combination electrode includes the preparation of 1) substrate;2) preparation of solution;3) carbon-coating is electroplated;4) transition metal oxide layer is electroplated;5) it cleans, is dry;Provide application of this kind of combination electrode in ultracapacitor simultaneously.The combination electrode of the present invention has excellent electric conductivity, higher quality specific capacitance and cyclical stability, and quality specific capacitance maximum is up to 1783Fg‑1, in 6Ag‑1Current density under cycle operation 2000 times, specific capacitance can remain the 84.4% of initial value, have broad application prospects.

Description

A kind of combination electrode, preparation method and application
Technical field
The present invention relates to a kind of combination electrodes and preparation method and application, belong to electronic material and devices field.
Background technology
Ultracapacitor (SC) is a kind of a kind of new type of energy storage device between traditional capacitor and electrochmical power source, tool Have that the charging time is short, have extended cycle life, broad application temperature range and the advantages such as economic and environment-friendly, closed extensively in various fields Note.With global warming, environmental pollution and the aggravation of energy shortage problem, it is badly in need of replacing traditional energy using clean energy resource, and Develop mating energy-storage system.SC is compared with traditional secondary cell and conventional dielectric capacitor, because of its high-energy density, soon The advantages that fast charge and discharge, can meet the needs of modern electronics industry development.According to charge-storage mechanism and electrode material not Together, SC common types have:Electrochemical capacitor in double electrode layer (EDLC) and fake capacitance capacitor.EDLC passes through the table in electrode material Face stored charge carrys out storing up electricity, has high power density, however energy density is relatively low, and specific capacitance is relatively low.Due to additional reversible oxygen Change reduction process, the specific capacitance of fake capacitance capacitor is one of research hotspot now far above EDLC.Transition metal oxide It is a kind of common fake capacitance electrode active material, there is low cost and advantages of environment protection, be with a wide range of applications.
Transition metal oxide for the electrode material of fake capacitance capacitor mainly includes RuO2、MnO2、Co3O4、NiO、 CuO etc., in addition, research shows that transition metal oxide/graphene combination electrode has higher specific capacitance and more preferably recycles Stability.When the transition metal oxide of nanoscale is dispersed on graphene, graphene can effectively prevent oxo transition metal The reunion of compound, on the other hand, graphene can increase effective contact area between transition metal oxide and electrolyte, improve Its electro-chemical activity;In addition, graphene has excellent mechanical property and electric conductivity as carrier material so that electrode is whole With prominent electrochemical stability and electric conductivity.
At this stage, the method for preparing transition metal oxide combination electrode has hydro-thermal method, thermal decomposition method, the precipitation method, electricity to sink Product, vapor phase method and solid phase method.A kind of existing Chinese patent " Ni-based MnO of foam2/ C combination electrode materials and preparation method thereof " (102,938 331 A of publication number CN) prepares carbon electrode using simple hydro-thermal method in foam nickel base, recycles electro-deposition Method prepares composite material.Carbon electrode obtained forms microcosmic spheric granules, and is overlapped mutually between particle, and this self aggregation shows As electrolyte can be caused to be difficult to penetrate into inside active material, so as to reduce electrode performance, and this hydro-thermal method experimental procedure is answered It is miscellaneous, experiment condition harshness and long preparation period.Separately there are Chinese patent " electrode of compound transition metal oxide containing manganese and its preparation side Method and application " (103996547 A of publication number) prepares the electrode of compound transition metal oxide containing manganese, electrode using galvanoplastic Quality specific capacitance be 313Fg-1, complex process and specific capacitance is relatively low.In addition, Jinbing Cheng et al. [Materials Letters 165 (2016) 231~234] prepares CoMn by the method for precipitating and annealing2O4Microballoon, and For electrode of super capacitor, method cost is higher and its quality specific capacitance is relatively low, only 788Fg-1
Invention content
In view of the above existing problems in the prior art, the present invention provides a kind of compound electrics for possessing better quality specific capacitance Pole also provides the preparation method and application of the combination electrode simultaneously.
To achieve these goals, the present invention provides a kind of combination electrodes, including substrate, the electroplating surface of the substrate There is carbon-coating, the electroplating surface of the carbon-coating has transition metal oxide layer;
The active layer of the combination electrode is in three-dimensional porous pleated structure, and the quality specific capacitance maximum of combination electrode is reachable 1783F·g-1
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Substrate is cleaned, removes oxide layer and greasy dirt;
2) preparation of solution:The additive solution containing carbon-based material is prepared, concentration range is 3~7mgmL-1
The electroplate liquid of transition-containing metal ion is prepared, the concentration range of transition metal ions is 3~5M in electroplate liquid;
3) carbon-coating is electroplated:In substrate after cleaning, carbon-coating is electroplated using the additive solution in step 2);
4) transition metal oxide layer is electroplated:In the substrate after carbon-coating is electroplated, continue using the electroplate liquid in step 2) Transition metal oxide layer is electroplated;
5) it cleans, is dry:It after plating, rinses through deionized water, dry at room temperature repeatedly, combination electrode is made.
As an improvement, in the step 1), the substrate used is nickel foam, conductive carbon paper or carbon fiber.
As an improvement, in the step 1), the substrate that uses is netted or fibrous.
As an improvement, in the step 3), when carbon-coating is electroplated, the temperature that uses is 40~85 DEG C, electroplating time 60 ~300s.
As an improvement, in the step 4), when transition metal oxide layer is electroplated, the temperature used for 40~80 DEG C, Electroplating time is 5~15s.
As an improvement, the carbon-based material in the step 2) is using any in graphene oxide, activated carbon, carbon nanotube Kind or several mixing.
As an improvement, the electroplate liquid in the step 2), using cabaltous nitrate hexahydrate, four chloride hydrate manganese, six hydrations three Two or more mixed solutions in iron chloride, Nickel dichloride hexahydrate, Gerhardite.
The present invention also provides application of this kind of combination electrode in ultracapacitor simultaneously.
The principle of the present invention is:Contain carbon material, after sonicated, carbon material in the additive solution that the present invention prepares In graphene dispersion it is uniform, in electroplating process, by electron exchange, part of hydroxyl and carboxyl functional group on graphene film It is reduced, so as to which graphene is reduced into redox graphene (rGO), these redox graphene pieces are constantly attached to base On bottom, planar structure is formed, is increased over time, the graphene film being reduced gradually increases, and part graphene film starts to stand Vertical to increase as time go on so as to form pleated structure, this pleated structure becomes that higher is thicker, by excellent conduction Property with pleated structure feature, this carbon-coating is very beneficial for the plating of later stage transition metal oxide layer.
After the completion of carbon-coating plating, it is placed into the electroplate liquid containing transition metal ions, it is molten again by reduction reaction Transition-metal cation in liquid obtains electronics and forms covalent bond with the carbon atom in rGO, is deposited in the rGO on pieces plated, Transition metal oxide layer is formed, in deposition process, Spatial Multi-Dimensional lamination is formed between the carbon atom in metallic atom and rGO Covalent bond, this aspect enhance the binding force between transition metal oxide layer and rGO layers, enhance the mechanically stable of electrode Property, on the other hand, the resistance between transition metal oxide layer and rGO layers is reduced, enhances the electric conductivity of electrode.With it is existing Technology is compared, the beneficial effects of the invention are as follows:
1) combination electrode of the invention has obtained monatomic by two-dimentional rGO by plating carbon-coating, transition metal oxide layer The product with the porous pleated structure of special three dimensions that layer and two-dimentional multi-element transition metal oxides are formed, however, passing Simple its microstructure of plating GO is two-dimentional paper-like in system technology, in addition, metal oxide electrode prepared by hydro-thermal method is micro- See the aggregation that structure is spheric granules, the electrode with special three dimensions pleated structure prepared by the present invention, carbon-coating conduct Skeleton has outstanding electric conductivity, and the multi-element transition metal oxides adhered to thereon have the specific surface area of super large, so as to have The catalytic activity of super large, overall structure porous, electrically conductive catalysis access.On the one hand this special construction is conducive to electronics in material internal On the other hand transmission, conducive to the ion transmission inside material void, therefore produces the quality specific capacitance of superelevation.
2) carbon-coating and polynary transiting metal oxidation is successfully electroplated using simple two steps galvanoplastic in the present invention in substrate Nitride layer, forms combination electrode, and the galvanoplastic experimental procedure of use is simple, it is easy to accomplish, and the addition of carbon-based additive is advantageous In the plating of transition metal oxide layer, porous pleated structure of the combination electrode obtained for three-dimensional, nanoscale transition metal Oxide and the compound of graphene can fill the respective material characteristics of part performance:The counterfeit of transition metal oxide can be made full use of Capacitive property, and the electric double layer capacitance performance of graphene can be made full use of so that combination electrode of the invention has excellent lead Electrically, higher quality specific capacitance and excellent cyclical stability, quality specific capacitance is up to 1783Fg-1, in 6Ag-1 Current density under after cycle operation 2000 times, specific capacitance still can remain the 84.4% of initial specific capacitance, have wide Application prospect.
Description of the drawings
Fig. 1 is the structure diagram of the combination electrode of the present invention;In figure:1st, substrate, 2, carbon-coating, 3, transition metal oxide Layer, as seen from the figure, combination electrode are three-dimensional porous pleated structure.
Fig. 2 is the interior atoms structure chart of the combination electrode of the present invention;Metallic atom in figure in transition metal oxide Spatial Multi-Dimensional lamination covalent bond is formd with the carbon atom in rGO.It can be seen from the figure that in transition metal atoms and rGO Carbon atom is combined closely by covalent bond.
Fig. 3 is the scanning electron microscope diagram that first electrode is made in the embodiment of the present invention 1;It can be seen from the figure that by Fold graphene forms layering porous structure for the self-standing transition metal oxide nano-slice of substrate.
Fig. 4 is the constant current charge-discharge curve that first electrode, second electrode are made in the embodiment of the present invention 1;It can be with from figure Find out, the constant current charge-discharge curve of two electrodes is triangular in shape symmetrical, shows good electric double layer performance, is in current density 1A·g-1When, first electrode biggest quality specific capacity is up to 1783Fg-1, the quality specific capacitance of second electrode is 863Fg-1
Fig. 5 is that first electrode, second electrode are made in the embodiment of the present invention 1 in 6Ag-1Current density under carry out constant current The change curve of quality specific capacitance during cycle charge-discharge 2000 times;As can be seen that first electrode specific capacitance is up to initial specific capacitance 84.4%, second electrode specific capacitance only reach initial specific capacitance 77.7%, i.e. the cyclical stability of first electrode is higher.
Specific embodiment
Understand to make the object, technical solutions and advantages of the present invention clearer, below by accompanying drawings and embodiments, to this Invention is further elaborated.However, it should be understood that the specific embodiments described herein are merely illustrative of the present invention, The range being not intended to restrict the invention.
Unless otherwise defined, all technical terms and scientific terms used herein are led with belonging to the technology of the present invention The normally understood meaning of technical staff in domain is identical, and used term is intended merely to retouch in the description of the invention herein State the purpose of specific embodiment, it is not intended that in the limitation present invention.
A kind of combination electrode, as shown in Figure 1, including substrate 1, the electroplating surface of the substrate 1 has carbon-coating 2, the carbon-coating 2 Electroplating surface have transition metal oxide layer 3;
The combination electrode is in three-dimensional porous pleated structure, and the quality specific capacitance maximum of combination electrode is up to 1783Fg-1
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Substrate is cleaned, removes oxide layer and greasy dirt;
2) preparation of solution:The additive solution containing carbon-based material is prepared, concentration range is 3~7mgmL-1
The electroplate liquid containing transition metal oxide is prepared, the concentration range of transition metal ions is 3~5M in electroplate liquid;
3) carbon-coating is electroplated:In substrate after cleaning, carbon-coating is electroplated using the additive solution in step 2);
4) transition metal oxide layer is electroplated:In the substrate after carbon-coating is electroplated, continue using the electroplate liquid in step 2) Transition metal oxide layer is electroplated;
5) it cleans, is dry:After plating, rinsed repeatedly with deionized water, after be dried at room temperature for get compound electric Pole.
As an improvement, in the step 1), the substrate used is nickel foam, conductive carbon paper or carbon fiber.
As an improvement, in the step 1), the substrate that uses is netted or fibrous.
As an improvement, in the step 3), when carbon-coating is electroplated, the temperature that uses is 40~85 DEG C, electroplating time 60 ~300s.
As an improvement, in the step 4), when transition metal oxide layer is electroplated, the temperature used for 40~80 DEG C, Electroplating time is 5~15s.
As an improvement, the carbon-based material in the step 2) is using graphene oxide (GO), activated carbon (AC), carbon nanotube Or several mixing any one of (CNT).
As an improvement, the transition metal ions in the step 2), using cabaltous nitrate hexahydrate (Co (NO3)2·6H2O)、 Four chloride hydrate manganese (MnCl2·4H2O), Iron(III) chloride hexahydrate (FeCl3·6H2O), Nickel dichloride hexahydrate (NiCl2· 6H2O), Gerhardite (Cu (NO3)2·3H2O the two or more mixing in).
The present invention also provides application of this kind of combination electrode in ultracapacitor simultaneously.
Embodiment 1
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Nickel foam is first taken, is cut into the sample of 1cm × 2cm, successively with hydrochloric acid (6M), acetone, ethyl alcohol It impregnates and is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, be then placed in drying for standby in nitrogen glove box;
2) preparation of solution:The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1AC and Tri- perchloric acid hydrate lithium (LiClO of 0.1M4·3H2O) mixed aqueous solution so that the total concentration of carbon-based material is 4 mg in solution ml-1, each 1h of ultrasonic mixing, magnetic agitation;
The electroplate liquid of transition-containing metal ion is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O and 1M chlorinations The mixed aqueous solution of sodium (NaCl) so that in electroplate liquid the total concentration of transition metal ions be 3M, ultrasonic mixing 10min, magnetic force Stir 1h;
3) carbon-coating is electroplated:In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2) Carbon-coating is plated, during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating;
4) transition metal oxide layer is electroplated:In the foam nickel base after carbon-coating is electroplated, continue using in step 2) Transition metal oxide layer is electroplated in electroplate liquid, and to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is kept 80 DEG C, time 12s of constant temperature, voltage are -1.2V, and one layer of hybrid transition metal oxide is electroplated;
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated Metal oxide layer, the electrode of gained are known as second electrode.
The scanning electron microscope diagram of first electrode is fig. 3, it is shown that by certainly station of the fold graphene for substrate Vertical transition metal oxide nano-slice forms layering porous structure.
The performance detection of the obtained combination electrode of the present invention:
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated When, active material in control first electrode and second electrode (on active material basidigitale, obtained by plating all material) matter Amount is 1 ± 0.2mg, according to multiple loop test as a result, as shown in figure 4, can be calculated, in 1Ag-1When, first electrode Quality specific capacitance is 1783Fg-1, the quality specific capacitance of second electrode is 863Fg-1.As can be seen that first electrode compared to Second electrode, quality specific capacitance increase 106%.Fig. 5 is first electrode, second electrode is in 6Ag-1Current density under, into After row constant current charge-discharge test 2000 times, the change curve of quality specific capacitance as seen from the figure, is surveyed by 2000 cycles Examination, the quality specific capacitance of first electrode are the 84.4% of its initial specific capacitance, and the quality specific capacitance of second electrode is its initial ratio The 77.7% of capacitance, it is possible thereby to find, the cyclical stability of first electrode is higher than second electrode.
In addition, with reference to the interior atoms structure chart of combination electrode in Fig. 2, the metallic atom in figure in transition metal oxide Spatial Multi-Dimensional lamination covalent bond is formd with the carbon atom in rGO.It can be seen from the figure that in transition metal atoms and rGO Carbon atom is combined closely by covalent bond.
Embodiment 2
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box;
2) preparation of solution:The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1AC and 0.1M LiClO4·3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 5mgml in solution-1, ultrasonic mixing, magnetic Power stirs each 1h;
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、2M NiCl2·6H2The mixed aqueous solution of O and 1M NaCl so that in electroplate liquid the total concentration of transition metal ions be 5M, ultrasonic mixing 10min, magnetic agitation 1h;
3) carbon-coating is electroplated:In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2) Carbon-coating is plated, during plating, electroplate liquid keeps 40 DEG C, time 300s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating;
4) transition metal oxide layer is electroplated:In the foam nickel base after carbon-coating is electroplated, continue using in step 2) Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected 40 DEG C, time 15s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated;
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment:
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 1481Fg-1, and the quality specific capacitance of second electrode is 981F g-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 50%.
Embodiment 3
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box;
2) preparation of solution:The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1CNT With 0.1M LiClO4·3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 5mgml in solution-1, ultrasonic mixing, Each 1h of magnetic agitation;
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.5M FeCl3·6H2The mixed aqueous solution of O and 1M NaCl so that the total concentration of transition metal ions is 3.5M in electroplate liquid, and ultrasound is mixed Close 10min, magnetic agitation 1h;
3) carbon-coating is electroplated:In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2) Carbon-coating is plated, during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating;
4) transition metal oxide layer is electroplated:In the foam nickel base after carbon-coating is electroplated, continue using in step 2) Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected 80 DEG C, time 5s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated;
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment:
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 960Fg-1, and the quality specific capacitance of second electrode is 501Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 91%.
Embodiment 4
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box;
2) preparation of solution:The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、2mg·ml-1CNT、 2mg·ml-1AC and 0.1M LiClO4·3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 7 mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation;
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.01M Cu(NO3)2·3H2The mixed aqueous solution of O and 1M NaCl so that the total concentration of transition metal ions is 3.01M in electroplate liquid, is surpassed Sound mixing 10min, magnetic agitation 1h;
3) carbon-coating is electroplated:In foam nickel base in step 1) after cleaning, using the additive solution electricity in step 2) Carbon-coating is plated, during plating, electroplate liquid keeps 85 DEG C, time 60s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference Electrode, platinized platinum are to electrode, and nickel foam is electroplated for the three-electrode method of working electrode.It is anti-with deionized water after plating Multiple rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the foam nickel electrode of carbon-coating;
4) transition metal oxide layer is electroplated:In the foam nickel base after carbon-coating is electroplated, continue using in step 2) Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected 50 DEG C, time 10s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated;
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment:
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 756Fg-1, and the quality specific capacitance of second electrode is 472Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 60%.
Embodiment 5
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Nickel foam is first taken, is cut into the sample of 1cm × 2cm, is impregnated with hydrochloric acid (6M), acetone, ethyl alcohol And it is cleaned by ultrasonic 10min, to remove oxide layer and greasy dirt, it is then placed in drying for standby in nitrogen glove box;
2) preparation of solution:Prepare the additive solution containing carbon-based material, 3mgml-1GO and 0.1M LiClO4·3H2O Mixed aqueous solution so that the total concentration of carbon-based material is 3mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation;
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.1M FeCl3·6H2O、0.1M NiCl2·6H2O、0.1M Cu(NO3)2·3H2The mixed aqueous solution of O and 1M NaCl so that plating The total concentration of transition metal ions is 3.3M, ultrasonic mixing 10min, magnetic agitation 1h in liquid;
3) carbon-coating is electroplated:Foam nickel base after cleaning in step 1) is suppressed into 5min under 2000Pa pressure in advance, is adopted Carbon-coating is electroplated with the additive solution in step 2), during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, voltage for- 1.2V, and using silver-silver chloride electrode as reference electrode, platinized platinum is to electrode, and nickel foam is carried out for the three-electrode method of working electrode Plating.After plating, rinsed repeatedly with deionized water, be placed in draught cupboard and spontaneously dry, obtain being electroplate with the foam of carbon-coating Nickel electrode;
4) transition metal oxide layer is electroplated:In the foam nickel base after carbon-coating is electroplated, continue using in step 2) Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the foam nickel electrode of carbon-coating as working electrode, during plating, electroplate liquid is protected 80 DEG C, time 12s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated;
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first Electrode, then piece of foam nickel substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition is only electroplated Metal oxide layer, the electrode of gained are known as second electrode.
The performance detection of combination electrode is made in the present embodiment:
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 916Fg-1, and the quality specific capacitance of second electrode is 663Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 38%.
Embodiment 6
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Conductive carbon paper is first taken, is cut into the sample of 1cm × 2cm, it is spare;
2) preparation of solution:The additive solution containing carbon-based material is prepared, includes 3mgml-1GO and 0.1M LiClO4· 3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 3mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation;
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O、0.01M Cu(NO3)2·3H2The mixed aqueous solution of O and 1M NaCl so that the total concentration of transition metal ions is 3.01M in electroplate liquid, is surpassed Sound mixing 10min, magnetic agitation 1h;
3) carbon-coating is electroplated:In step 1) on conductive carbon paper, carbon-coating, plating are electroplated using the additive solution in step 2) When, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and using silver-silver chloride electrode as reference electrode, platinized platinum is To electrode, conductive carbon paper is electroplated for the three-electrode method of working electrode.After plating, rinsed, put repeatedly with deionized water It is spontaneously dried in draught cupboard, obtains being electroplate with the conductive carbon paper electrode of carbon-coating;
4) transition metal oxide layer is electroplated:In the conductive carbon paper substrate after carbon-coating is electroplated, continue using in step 2) Electroplate liquid plating transition metal oxide layer, first to be coated with the conductive carbon paper electrode of carbon-coating as working electrode, during plating, plating Liquid keeps 80 DEG C, time 12s of constant temperature, and voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated;
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first Electrode, then a piece of conductive carbon paper substrate is separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, only plating mixed Metal oxide layer is crossed, the electrode of gained is known as second electrode.
The performance detection of combination electrode is made in the present embodiment:
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 303Fg-1, and the quality specific capacitance of second electrode is 158Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 91%.
Embodiment 7
A kind of preparation method of combination electrode, specifically includes following steps:
1) preparation of substrate:Carbon fiber is first taken, carbon fiber is cut into the sample of long 2cm, with ultrasound after acetone soak 2h 5min is cleaned, dries, takes out spare under the conditions of 60 DEG C;
2) preparation of solution:The additive solution containing carbon-based material is prepared, includes 3mgml-1GO、0.1M LiClO4· 3H2O mixed aqueous solutions so that the total concentration of carbon-based material is 3mgml in solution-1, each 1h of ultrasonic mixing, magnetic agitation;
The electroplate liquid containing transition metal oxide is prepared, includes 1M Co (NO3)2·6H2O、2M MnCl2·4H2O and 1M The mixed aqueous solution of NaCl so that in electroplate liquid the total concentration of transition metal ions be 3M, ultrasonic mixing 10min, magnetic agitation 1h;
3) carbon-coating is electroplated:On carbon fiber in step 1) after cleaning, using the additive solution carbon electroplating in step 2) Layer, during plating, electroplate liquid keeps 70 DEG C, time 100s of constant temperature, and voltage is -1.2V, and electric by reference of silver-silver chloride electrode Pole, platinized platinum are to electrode, and carbon fiber is electroplated for the three-electrode method of working electrode.After plating, with deionized water repeatedly Rinsing, is placed in draught cupboard and spontaneously dries, obtain being electroplate with the carbon fiber electrode of carbon-coating;
4) transition metal oxide layer is electroplated:In the carbon fiber substrates after carbon-coating is electroplated, continue using in step 2) Transition metal oxide layer is electroplated in electroplate liquid, and first to be coated with the carbon fiber electrically of carbon-coating extremely working electrode, during plating, electroplate liquid is protected 80 DEG C, time 12s of constant temperature is held, voltage is -1.2V, and one layer of hybrid transition metal oxide is electroplated;
5) be electroplated after, rinsed repeatedly with deionized water, after be dried at room temperature for, the electrode being prepared is known as first Electrode, then a carbon fiber substrates are separately taken, relative to the preparation process of first electrode, carbon-coating is not electroplated, mixed transition gold is only electroplated Belong to oxide skin(coating), the electrode of gained is known as second electrode.
The performance detection of combination electrode is made in the present embodiment:
Using combination electrode obtained as working electrode, platinized platinum is to electrode, and mercury-mercuric oxide electrode is reference electrode, 1M's Potassium hydroxide aqueous solution is electrolyte, carries out capacitance measurement using constant current charge-discharge system, voltage window is 0~0.55V, is electroplated When, control first electrode is 1 ± 0.2mg with active material quality in second electrode, according to multiple loop test as a result, calculating It can obtain, in 1Ag-1When, first electrode quality specific capacitance is 498Fg-1, and the quality specific capacitance of second electrode is 332Fg-1.As can be seen that first electrode, compared to second electrode, quality specific capacitance improves 50%.
The specific performance testing result of the various embodiments described above is as shown in table 1 below.
The performance test results of electrode in 1 each embodiment of table
Carbon-coating, transition metal oxide layer is electroplated it is found that the combination electrode of the present invention passes through with reference to the testing result of table 1, It has obtained being made of two-dimentional rGO monoatomic layers and two-dimentional multi-element transition metal oxides layer porous with special three dimensions The product of pleated structure, however, the GO formed using conventional plating techniques, paper-like of the microstructure for two dimension, hydro-thermal legal system Its microstructure of standby metal oxide electrode is the aggregation of spheric granules, and prepared by the present invention has special three dimensions fold The electrode of structure, carbon-coating have outstanding electric conductivity as skeleton, and the multi-element transition metal oxides adhered to thereon have super Big specific surface area, so as to the catalytic activity with super large, on the one hand overall structure porous, electrically conductive catalysis access exists conducive to electronics Material internal transmits, and on the other hand, is transmitted, therefore produce higher quality specific capacitance conducive to the ion of material pore interior.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention Any modification, equivalent replacement or improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.

Claims (9)

1. a kind of combination electrode, which is characterized in that including substrate (1), the electroplating surface of the substrate (1) has carbon-coating (2), described The electroplating surface of carbon-coating (2) has transition metal oxide layer (3);
The combination electrode is in three-dimensional porous pleated structure, and the quality specific capacitance of combination electrode reaches as high as 1783Fg-1
2. the preparation method of combination electrode described in a kind of claim 1, which is characterized in that specifically include following steps:
1) preparation of substrate:Substrate is cleaned, removes oxide layer and greasy dirt;
2) preparation of solution:The additive solution containing carbon-based material is prepared, concentration range is 3~7mgml-1
The electroplate liquid of transition-containing metal ion is prepared, the concentration range of transition metal ions is 3~5M in electroplate liquid;
3) carbon-coating is electroplated:In substrate after cleaning, carbon-coating is electroplated using the additive solution in step 2);
4) transition metal oxide layer is electroplated:In the substrate after carbon-coating is electroplated, continue using the electroplate liquid plating in step 2) Transition metal oxide layer;
5) it cleans, is dry:It after plating, rinses through deionized water, dry at room temperature repeatedly, combination electrode is made.
3. the preparation method of a kind of combination electrode according to claim 2, which is characterized in that in the step 1), use Substrate be nickel foam, conductive carbon paper or carbon fiber.
4. the preparation method of a kind of combination electrode according to Claims 2 or 3, which is characterized in that in the step 1), adopt Substrate is netted or fibrous.
5. a kind of preparation method of combination electrode according to claim 2, which is characterized in that in the step 3), electricity When plating carbon-coating, for the temperature used for 40~85 DEG C, electroplating time is 60~300s.
6. a kind of preparation method of combination electrode according to claim 2, which is characterized in that in the step 4), electricity When plating transition metal oxide layer, for the temperature used for 40~80 DEG C, electroplating time is 5~15s.
7. the preparation method of a kind of combination electrode according to claim 2, which is characterized in that carbon-based in the step 2) Material is using any one of graphene oxide, activated carbon, carbon nanotube or several mixing.
8. the preparation method of a kind of combination electrode according to claim 2 or 7, which is characterized in that in the step 2) Electroplate liquid, using cabaltous nitrate hexahydrate, four chloride hydrate manganese, Iron(III) chloride hexahydrate, Nickel dichloride hexahydrate, Gerhardite In two or more mixed solutions.
9. described in a kind of claim 1 or any one of claim 2-8 combination electrode made from the preparation method is in super electricity Application in container.
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