CN104576079A - Metallic oxide nanowire coil/active carbon fiber composite electrode material and preparation thereof - Google Patents
Metallic oxide nanowire coil/active carbon fiber composite electrode material and preparation thereof Download PDFInfo
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- CN104576079A CN104576079A CN201410803283.3A CN201410803283A CN104576079A CN 104576079 A CN104576079 A CN 104576079A CN 201410803283 A CN201410803283 A CN 201410803283A CN 104576079 A CN104576079 A CN 104576079A
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- carbon fiber
- activated carbon
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- metal oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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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 provides a metallic oxide nanowire coil/active carbon fiber composite electrode material and a preparation method thereof. The metallic oxide nanowire coil/active carbon fiber composite electrode material comprises active carbon fiber, cobalt oxide and nickel oxide, wherein the cobalt oxide and nickel oxide grow on the surface of the active carbon fiber in a covering manner in the form of nanowire or nanowire coil. The electrode material disclosed by the invention adopts a fluffy network structure, has large specific area and is in full contact with electrolyte; electrolyte ions have a short moving path, so that high convenience and rapidity are realized. Metallic oxides have larger surfaces and more active sites to participate in electrode reaction, so that the electric charge storage capacity and the power performance of the electrode are improved; in addition, the active carbon fiber can store electric charges, can also serve as a matrix to be easily processed into the electrode and is not dense. The composite electrode expresses the advantages of two types of electrode materials and overcomes the defects of a single electrode material.
Description
Technical field
The invention belongs to material and electrochemical field, relate to a kind of preparation method of electrode material for super capacitor.
Background technology
As a kind of Novel energy storage apparatus, the application of ultracapacitor in electric power, illumination, electronics, traffic, automobile and other industries is more and more extensive.The many merits such as the ultracapacitor life-span is long, charging is fast, power-performance is good, use cost is low, making it as having great potential in Novel mobile power source and vehicle drive power, being expected to the status progressively replacing battery.But compare battery, the energy density of ultracapacitor is too low, is only 1/tens of battery.The energy density of capacitor depends on the performance of electrode material and electrolyte, and electrode material is more crucial, and its ability storing electric charge is both relevant with the chemical species of material, also relevant with the physical aspect structure of material.
Electrode material for super capacitor has two kinds of accumulate mechanism: form electric capacity at electrode surface with electric double layer, or reversible faraday occurs reacts formation pseudo-capacitance.The height of electrode material charge storage ability, can touch the surface size of electrolyte with it, or the amount of substance that can participate in occurring electrochemical reaction on surface is directly proportional.The specific area of electrode is larger, and its charge storage ability is stronger.Therefore, greatly mainly with the electrode material of the very large porous charcoal of specific area as ultracapacitor, its ability storing electric charge is far above traditional flat capacitor device.
In order to improve the energy density (or ratio capacitance) of ultracapacitor further, the technological approaches of main employing be improve further capacitor electrode material specific area and regulate suitable in/micropore ratio, or adopt transition metal oxide/conductive organic polymer do electrode.Chinese patent CN1810637A and ZL200410021684.X individually discloses the method that active carbon with high specific surface area and mesopore activated carbon fiber prepare electrode material; It is that particle random loading is on powdered activated carbon that patent CN1402280A discloses Mn, Co metal oxide, patent CN103114434A discloses several nano-metal-oxide doped polymer modification activities carbon fiber electrode, and these methods all make electrode ratio capacitance be significantly improved.
Summary of the invention
Technical problem to be solved by this invention be by metal oxide with nano wire or nano wire dense growth on activated carbon fiber surface, make a kind of combination electrode material having fluffy network configuration.
In order to solve the problems of the technologies described above, the invention provides a kind of metal oxide nano-wire group/activated carbon fiber combination electrode material, it is characterized in that, comprise the oxide of activated carbon fiber, cobalt and nickel, described cobalt and the oxide of nickel with the coated growth of form of nano wire or nanowire cluster on activated carbon fiber surface.
Present invention also offers the preparation method of above-mentioned metal oxide nano-wire group/activated carbon fiber combination electrode material, it is characterized in that, concrete steps comprise:
Step 1: by the solution that impregnated in after activated carbon fiber clean dry containing cobalt ions and nickel ion 0.5 ~ 5 hour, then proceed in hydrothermal reactor, add ammonium salt, 50 ~ 450 DEG C of reactions 1 ~ 25 hour;
Step 2: take out activated carbon fiber and wash, 150 ~ 500 DEG C of calcinings 1 ~ 10 hour, cobalt salt and nickel salt were converted into oxide, obtain metal oxide nano-wire group/activated carbon fiber combination electrode material.
Preferably, the described solution containing cobalt ions and nickel ion to be weight concentration be 0.01 ~ 25% cobalt salt and weight concentration be the aqueous solution of the nickel salt of 0.01 ~ 25%.
More preferably, the weight concentration of described cobalt salt is 0.01 ~ 5%
More preferably, the weight concentration of described nickel salt is 0.01 ~ 5%.
More preferably, described cobalt salt is at least one in cobaltous sulfate and cobalt chloride.
More preferably, described nickel salt is at least one in nickel chloride and nickel acetate.
Preferably, described ammonium salt is ammonium chloride, and its addition is 0.1 ~ 5% of the described solution weight containing cobalt ions and nickel ion.
Preferably, described activated carbon fiber is made by least one in viscose glue, acrylic fibers, phenolic aldehyde and pitch fibers.
Preferably, the contour structures of described activated carbon fiber is long fibre, short fiber, fabric or felt.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention is surperficial at activated carbon fiber with the form growth of nano wire or a ball of string metal oxide, and this electrode material has fluffy network configuration, and specific area is large, and abundant with the contact of electrolyte, electrolyte ion mobile route is short, convenient and swift.Metal oxide has larger surface and more active sites to participate in electrode reaction, thus improves ability and the power-performance of electrode storage electric charge.
2, existing employing metal oxide does in the technology of electrode material, and metal oxide is powdery, graininess or block to mix with matrix, or Random Load is on matrix, then moors with metal and be pressed into combination electrode.This electrode structure is closely knit, and surface area is little.On matrix, the amount of portative metal oxide is limited, or the metal oxide of load is too abundant, and inner oxide can not effectively participate in electrochemical reaction.In the present invention, metal oxide becomes nano-scale fiber shape, and specific area is large; Structure is fluffy simultaneously, is conducive to the fast transferring of electrolyte ion.In addition, the surface that activated carbon fiber itself both can be huge stores electric charge, can be easy to be processed into electrode as matrix again, can not be closely knit.Because metal oxide can have higher charge storage ability by specific activity carbon fiber, but power-performance is poor, and is difficult to shaping, and activated carbon fiber is then contrary.The two is combined, just can give full play to the advantage of two kinds of electrode materials, overcome the deficiency of unitary electrode.This electrode material made is carried out scanning electron microscopic observation and electrochemical property test, there is these advantages really.
Accompanying drawing explanation
Fig. 1 a and 1b is the surface topography of the metal oxide nano-wire group/activated carbon fiber combination electrode material under different amplification in embodiment 1.
Fig. 2 is the cyclic voltammetry curve of combination electrode material under different scanning voltage speed in embodiment 1.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
A kind of metal oxide nano-wire group/activated carbon fiber combination electrode material, comprises the oxide of activated carbon fiber, cobalt and nickel, described cobalt and the oxide of nickel with the coated growth of form of nano wire or nanowire cluster on activated carbon fiber surface.
Present invention also offers the preparation method of above-mentioned metal oxide nano-wire group/activated carbon fiber combination electrode material, concrete steps are
Step 1: cobaltous sulfate and nickel acetate are added to the water to make containing weight concentration be the mixed aqueous solution of the cobaltous sulfate of 0.5% and the nickel acetate of 0.3%, general industry activated carbon fiber Nomex (as Anhui Jia Liqi carbon fiber Co., Ltd product) watery hydrochloric acid and deionized water are cleaned, 1 hour is immersed in the mixed aqueous solution of above-mentioned cobaltous sulfate and nickel acetate after oven dry, then be transferred to together in hydrothermal reactor, add ammonium chloride, its addition was 0.5% of the weight of the mixed aqueous solution of described cobaltous sulfate and nickel acetate, 90 DEG C of reactions 15 hours;
Step 2: after reaction terminates, reactor is cooled to room temperature, takes out activated carbon fiber, cleans with deionized water.Then be placed on 250 DEG C of calcinings 8 hours in tube furnace, cobalt salt and nickel salt are converted into oxide.Take out after cooling, namely obtain described metal oxide nano-wire group/activated carbon fiber combination electrode material.
As shown in Figure 1, be the stereoscan photograph of metal oxide nano-wire group/activated carbon fiber combination electrode material, the diameter of oxide silk thread is about tens nanometers.Nanometer silk thread is completely coated by activated carbon fiber, forms fluffy network channel between silk thread, and this is all conducive to the migration velocity of increasing specific surface area and electrolyte ion, thus improves the power-performance of electrode ratio capacitance and energy density and capacitor.
As shown in Figure 2, be the cyclic voltammetry curve of this combination electrode material under different scanning voltage speed.The ratio capacitance that this electrode material records when current density is 5mA reaches 557F/g, is significantly better than 100 ~ 200F/g of existing porous carbon electrode.
Claims (10)
1. metal oxide nano-wire group/activated carbon fiber combination electrode material, it is characterized in that, comprise the oxide of activated carbon fiber, cobalt and nickel, described cobalt and the oxide of nickel with the coated growth of form of nano wire or nanowire cluster on activated carbon fiber surface.
2. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material according to claim 1, it is characterized in that, concrete steps comprise:
Step 1: by the solution that impregnated in after activated carbon fiber clean dry containing cobalt ions and nickel ion 0.5 ~ 5 hour, then proceed in hydrothermal reactor, add ammonium salt, 50 ~ 450 DEG C of reactions 1 ~ 25 hour;
Step 2: take out activated carbon fiber and wash, 150 ~ 500 DEG C of calcinings 1 ~ 10 hour, cobalt salt and nickel salt were converted into oxide, obtain metal oxide nano-wire group/activated carbon fiber combination electrode material.
3. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 2, it is characterized in that, the described solution containing cobalt ions and nickel ion to be weight concentration be 0.01 ~ 25% cobalt salt and weight concentration be the aqueous solution of the nickel salt of 0.01 ~ 25%.
4. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 3, it is characterized in that, the weight concentration of described cobalt salt is 0.01 ~ 5%.
5. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 3, it is characterized in that, the weight concentration of described nickel salt is 0.01 ~ 5%.
6. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 3, is characterized in that, described cobalt salt is at least one in cobaltous sulfate and cobalt chloride.
7. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 3, is characterized in that, described nickel salt is at least one in nickel chloride and nickel acetate.
8. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 2, it is characterized in that, described ammonium salt is ammonium chloride, and its addition is 0.1 ~ 5% of the described solution weight containing cobalt ions and nickel ion.
9. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 2, it is characterized in that, described activated carbon fiber is made by least one in viscose glue, acrylic fibers, phenolic aldehyde and pitch fibers.
10. the preparation method of metal oxide nano-wire group/activated carbon fiber combination electrode material as claimed in claim 2, it is characterized in that, the contour structures of described activated carbon fiber is long fibre, short fiber, fabric or felt.
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| CN201410803283.3A CN104576079A (en) | 2014-12-18 | 2014-12-18 | Metallic oxide nanowire coil/active carbon fiber composite electrode material and preparation thereof |
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| CN201410803283.3A CN104576079A (en) | 2014-12-18 | 2014-12-18 | Metallic oxide nanowire coil/active carbon fiber composite electrode material and preparation thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365210A (en) * | 2016-08-29 | 2017-02-01 | 浙江工业大学 | Preparation and application of shape-controlled cobaltosic oxide nano array |
| CN110607052A (en) * | 2019-09-23 | 2019-12-24 | 广东生益科技股份有限公司 | Prepreg, laminated board and printed circuit board |
| CN114927353A (en) * | 2022-02-16 | 2022-08-19 | 上海应用技术大学 | CF/WO 3 /TiO 2 Composite material and preparation and application thereof |
Citations (1)
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| CN103288416A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Modified three-dimensional fiber-based aerogel material and preparation method thereof |
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- 2014-12-18 CN CN201410803283.3A patent/CN104576079A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103288416A (en) * | 2013-05-27 | 2013-09-11 | 东华大学 | Modified three-dimensional fiber-based aerogel material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XINHUI XIA等: "High-Quality Metal Oxide Core/Shell Nanowire Arrays on Conductive Substrates for Electrochemical Energy Storage", 《ACS NANO》 * |
| 仲林: "钴/镍、钴/锰二元氧化物与ACF复合电极结构及电容特性的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106365210A (en) * | 2016-08-29 | 2017-02-01 | 浙江工业大学 | Preparation and application of shape-controlled cobaltosic oxide nano array |
| CN110607052A (en) * | 2019-09-23 | 2019-12-24 | 广东生益科技股份有限公司 | Prepreg, laminated board and printed circuit board |
| CN110607052B (en) * | 2019-09-23 | 2022-06-03 | 广东生益科技股份有限公司 | Prepreg, laminated board and printed circuit board |
| CN114927353A (en) * | 2022-02-16 | 2022-08-19 | 上海应用技术大学 | CF/WO 3 /TiO 2 Composite material and preparation and application thereof |
| CN114927353B (en) * | 2022-02-16 | 2024-01-26 | 上海应用技术大学 | CF/WO 3 /TiO 2 Composite material, preparation and application thereof |
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Application publication date: 20150429 |