CN103646788A - Nickel oxalate based asymmetrical supercapacitor and preparation method thereof - Google Patents
Nickel oxalate based asymmetrical supercapacitor and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of capacitor preparation and relates to a nickel oxalate based asymmetrical supercapacitor and a preparation method thereof. The nickel oxalate based asymmetrical supercapacitor comprises a positive pole piece, a negative pole piece, electrolyte, an isolating membrane and a packaging film and is characterized in that the positive pole piece is made from a nickel/di-hydrated nickel oxalate nanocomposite material, a substrate is made of a flat board or foamed nickel, a coating layer is a di-hydrated nickel oxalate film with a nano structure and 50-100micron thickness, the positive pole piece is an activated carbon pole piece, and the electrolyte is a 1-6mol/L potassium hydroxide or sodium hydroxide solution. The preparation method of the nickel oxalate based asymmetrical supercapacitor comprises the steps of preparing the positive pole piece and the negative pole piece and assembling and packaging the capacitor. The nickel oxalate based asymmetrical supercapacitor is large in specific capacitance and high in specific power and specific energy density, and the preparation method is simple, easy and high in controllability.
Description
Technical field
The invention belongs to capacitor preparation field, particularly Ni-based asymmetric ultracapacitor of a kind of oxalic acid and preparation method thereof.
Background technology
Ultracapacitor (Super Capacitor) is a kind of novel energy-storing element between conventional capacitor and chemical cell, has the feature of the specific energy that specific power that traditional capacitor is high and chemical cell are high concurrently.Be a kind of energy storing device of efficient, practical, environmental protection, its superior performance obtains the attention of each side.According to different standards, ultracapacitor has different classification.According to the mechanism of different store electrical energy, ultracapacitor is divided into two classes: a class is double electric layer capacitor, the generation of its electric capacity is mainly the double electric layer capacitor (Electric Double Capacitors, EDLC) based on interfacial electric double layer principle between high-specific surface area material with carbon element and solution; Another kind of is Faraday pseudo-capacitance device (Faraday Pseudo-capacitor), the generation of its electric capacity is in the two dimension or accurate two-dimensional space based on electrode material surface or body phase, electroactive material carries out underpotential deposition, there is highly reversible chemisorbed-desorption or oxidation-reduction reaction, produce the electric capacity relevant with electrode charge current potential.
Fake capacitance material comprises conducting polymer, such as polypyrrole, polythiophene, polyaniline etc., also has metal oxide, such as RuO
2, MnO
2, Co
3o
4deng.Metal oxide, compared to active carbon, has higher energy density, and compared to conducting polymer, electrochemical stability is higher.The form of metal oxide has a great impact electric capacity, the electric capacity of nanostructure is much larger than block, this is because nanostructure has larger specific area, makes more active material can form electric double layer or redox reaction occurs and produces larger electric capacity.
The double electric layer capacitor that the porous activated carbon of take is electrode material can have good power-performance, but has lower specific energy; Take metal oxide (as ruthenium-oxide) although have higher specific energy as the fake capacitance device of electrode material, and its cost of material is higher; Another kind ofly take the fake capacitance device that polymer (as polyaniline) is electrode material and also there is higher specific energy, but its cycle performance and electric conductivity are poor.
In order to obtain higher energy density and power density simultaneously, people start to design novel asymmetric ultracapacitor, and a utmost point of capacitor is double layer electrodes, and another is Faraday pseudo-capacitance electrode very.Non-symmetrical electrochemical supercapacitor combines the advantage of two class electrochemical capacitors, can meet better the whole requirement of load to the energy density of power-supply system and power density in practical application.
The method of preparing metal oxide electrode mainly contains electrochemical deposition, hydro thermal method, template, chemical vapour deposition (CVD) etc.For example, in Chinese patent 201210142685, then the use hydro-thermal legal systems such as Zhang Kejin are made according to a certain ratio slurry by itself and conductive agent, binding agent for manganese dioxide or nano-manganese dioxide/absorbent charcoal composite material and are coated in nickel foam, make positive pole.The method is wanted distributed operation, length consuming time, complicated operation; The method that electrode is prepared in brushing not as growth in situ uniform and stable.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of Ni-based asymmetric ultracapacitor of oxalic acid and preparation method based on nickel/bis-oxalic acid hydrate nickel nano composite material is provided.
The present invention is achieved in the following ways:
The Ni-based asymmetric ultracapacitor of a kind of oxalic acid, comprise anode pole piece, cathode pole piece, electrolyte, barrier film and packaging film, electrolyte is filled in the closed container of packaging film formation, and anode pole piece, cathode pole piece are placed in electrolyte, and anode pole piece, cathode pole piece are separated by barrier film; It is characterized in that anode pole piece is nickel/bis-oxalic acid hydrate nickel nano composite material, substrate is the nickel of flat board or foam form, and coating layer is two oxalic acid hydrate nickel retes of nanostructure, thickness 50 nanometer～100 micron; Cathode pole piece is active carbon pole piece; Electrolyte is potassium hydroxide or the sodium hydroxide solution of 1～6mol/L.
The preparation method of the Ni-based asymmetric ultracapacitor of above-mentioned oxalic acid, comprises the preparation of positive/negative plate, the assembling of capacitor and encapsulation, it is characterized in that comprising the following steps:
(1) prepare nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece; According to the concentration preparation oxalic acid solution of 0.01～1.5mol/L; Flat board or nickel foam are placed in to above-mentioned prepared oxalic acid solution, by constant voltage method or galvanostatic method, carry out anodized, at metallic nickel Surface Creation thickness, be two oxalic acid hydrate nickel coating layers of 50 nanometer～100 micron, make nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece;
(2) prepare activated carbon negative electrode pole piece; According to the ratio of 8:1:1, weigh active carbon, carbon black and Kynoar and mix standby; In the mixture of active carbon, carbon black and Kynoar, add appropriate n-methlpyrrolidone as solvent, stir, obtain the uniform sizing material with certain viscosity, brushing is in the nickel foam of having sheared; In drying box, 80 degrees Celsius are dried 4～5 hours, make activated carbon negative electrode pole piece, take out standby;
(3) assembling capacitor: get activated carbon negative electrode pole piece prepared by nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece prepared by step (1) and step (2), centre adds barrier film, stack alignment relatively, pack in packaging film, splash into electrolyte, anode pole piece exposes upper metal part to be connected wire with cathode pole piece.
The preparation method of the Ni-based asymmetric ultracapacitor of above-mentioned oxalic acid, is characterized in that the reaction condition of constant voltage method in step (1) is: 1～100 volt of reaction potential, 10 seconds～1 hour reaction time, reaction temperature-10～90 degree Celsius.The reaction condition of galvanostatic method is: kinetic current 10 milliamperes～30 peaces, 10 seconds～1 hour reaction time, reaction temperature-10～90 degree Celsius.
Ni-based asymmetric ultracapacitor of oxalic acid of the present invention and preparation method thereof has the following advantages:
(1) the Ni-based asymmetric capacity of super capacitor of oxalic acid of the present invention is large, and specific energy, specific power are high; Ultracapacitor nickel/bis-oxalic acid hydrate used nickel nano composite material pole piece adopts the metallic nickel of flat board or foam form to do substrate, can be simultaneously as support substrates and current collector, simplify the manufacturing process of ultracapacitor, the load that has alleviated ultracapacitor;
(2) preparation method of the present invention, thickness and the capacitance size of alternative control capacitor, the parameter such as concentration, volume and the proportioning of electrolyte and temperature, voltage, reaction time, electrode spacing while preparing by controlling nickel/bis-oxalic acid hydrate nickel nano composite material electrode, regulate structure and the thickness of the oxide generating, to reach the object of control capacitor capacitance size, controllability is high;
(3) preparation method of the present invention, simple, applied widely.
Embodiment
Provide five most preferred embodiments of the present invention below, but institute of the present invention protection range is not limited to this.
Embodiment 1
The Ni-based asymmetric ultracapacitor of oxalic acid, comprises anode pole piece, cathode pole piece, electrolyte, barrier film and packaging film, and electrolyte is filled in the closed container of packaging film formation, and anode pole piece, cathode pole piece are placed in electrolyte, by barrier film, are separated.Described anode pole piece is nickel foam/bis-oxalic acid hydrate nickel nano composite material, and substrate is the nickel foam of 2 millimeters thick, and coating layer is the metal oxide rete of nanostructure.Described cathode pole piece is active carbon pole piece.Electrolyte is potassium hydroxide solution.
The preparation method of the Ni-based asymmetric ultracapacitor of above-mentioned oxalic acid, comprises the preparation of positive/negative plate, the assembling of capacitor and encapsulation, and concrete steps are as follows:
A kind of preparation method of nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece is as follows:
(1) oxalic acid solution of preparation 0.5mol/L is standby;
(2) by 2 centimetres of 2 cm x, the nickel foam of 2 millimeters thick is placed in (1) described electrolyte, connects wire, and nickel foam is done positive pole, and dull and stereotyped nickel sheet is done negative pole;
(3) under 50 volts of voltages of subzero 10 degrees Celsius of constant potentials, nickel foam is carried out to anodized, react 5 minutes, make nickel foam/bis-oxalic acid hydrate nickel composite material.Two oxalic acid hydrate nickel are evenly distributed on nickel foam ligament.
A kind of preparation method of activated carbon negative electrode pole piece is as follows:
(1) according to the ratio of 8:1:1, weigh active carbon, carbon black and Kynoar (PVDF) standby;
(2) add n-methlpyrrolidone appropriate, stir, brushing is in the nickel foam of having sheared;
(3) in drying box 80 degrees Celsius dry 5 hours, take out standby.
The assembling of capacitor:
(1) potassium hydroxide solution of preparation 2mol/L is standby;
(2) by the activated carbon negative electrode pole piece of preparation and the simple metal Partial Shear of nickel foam/bis-oxalic acid hydrate nickel nano composite material anode pole piece, make integral body be " 7 " type, with separated two electrodes of barrier film, stack alignment, pack in packaging film, splash into electrolyte, pole piece exposes upper metal part to connect wire, encapsulation.
Embodiment 2
Ni-based asymmetric ultracapacitor of a kind of oxalic acid and preparation method thereof, except using the oxalic acid solution of 1mol/L as electrolyte in the preparation of nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece, under 30 volts of voltages of subzero 10 degrees Celsius of constant potentials, nickel foam is carried out to anodized 10 minutes, capacitor assembling adopts outside the potassium hydroxide solution of 4mol/L, and all the other are with embodiment 1.
Embodiment 3
Ni-based asymmetric ultracapacitor of a kind of oxalic acid and preparation method thereof, except using the oxalic acid solution of 0.2mol/L as electrolyte in the preparation of nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece, under 50 volts of voltages of subzero 5 degrees Celsius of constant potentials, flat board is carried out to anodized 15 minutes, capacitor assembling adopts outside the sodium hydroxide solution of 1mol/L, and all the other are with embodiment 1.
Embodiment 4
Ni-based asymmetric ultracapacitor of a kind of oxalic acid and preparation method thereof, except using the oxalic acid solution of 0.6mol/L as electrolyte in the preparation of nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece, under 40 volts of voltages of subzero 5 degrees Celsius of constant potentials, dull and stereotyped nickel is carried out to anodized 10 minutes, capacitor assembling adopts outside the sodium hydroxide solution of 6mol/L, and all the other are with embodiment 1.
Embodiment 5
Ni-based asymmetric ultracapacitor of a kind of oxalic acid and preparation method thereof, except using the oxalic acid solution of 0.5mol/L as electrolyte in the preparation of nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece, under 40 volts of voltages of 25 degrees Celsius of constant potentials, dull and stereotyped nickel is carried out to anodized 10 minutes, capacitor assembling adopts outside the potassium hydroxide solution of 6mol/L, and all the other are with embodiment 1.
Claims (4)
1. the Ni-based asymmetric ultracapacitor of oxalic acid, comprise anode pole piece, cathode pole piece, electrolyte, barrier film and packaging film, electrolyte is filled in the closed container of packaging film formation, and anode pole piece, cathode pole piece are placed in electrolyte, and anode pole piece, cathode pole piece are separated by barrier film; It is characterized in that anode pole piece is nickel/bis-oxalic acid hydrate nickel nano composite material, substrate is the nickel of flat board or foam form; Coating layer is two oxalic acid hydrate nickel retes of nanostructure, and thickness is 50 nanometer～100 micron; Cathode pole piece is active carbon pole piece; Electrolyte is potassium hydroxide or the sodium hydroxide solution of 1～6mol/L.
2. the preparation method of the Ni-based asymmetric ultracapacitor of a kind of oxalic acid according to claim 1, comprises the preparation of positive/negative plate, the assembling of capacitor and encapsulation, it is characterized in that comprising the following steps:
(1) prepare nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece: according to the concentration preparation oxalic acid solution of 0.01～1.5mol/L; Flat board or nickel foam are placed in to above-mentioned prepared oxalic acid solution, with constant-voltage method or constant flow method, carry out anodized, at metallic nickel Surface Creation thickness, be two oxalic acid hydrate nickel coating layers of 50 nanometer～100 micron, make nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece;
(2) prepare activated carbon negative electrode pole piece: according to the ratio of 8:1:1, weigh active carbon, carbon black and Kynoar and mix standby; In the mixture of active carbon, carbon black and Kynoar, add appropriate n-methlpyrrolidone as solvent, stir, obtain the uniform sizing material with viscosity, brushing is in the nickel foam of having sheared; In drying box, 80 degrees Celsius are dried 4～5 hours, make activated carbon negative electrode pole piece, take out standby;
(3) assembling capacitor: get nickel/bis-oxalic acid hydrate nickel nano composite material anode pole piece and activated carbon negative electrode pole piece, centre adds barrier film, stack alignment relatively, packs in packaging film, splashes into electrolyte, and pole piece exposes upper metal part to connect wire.
3. the preparation method of the Ni-based asymmetric ultracapacitor of oxalic acid according to claim 2, is characterized in that the reaction condition of step (1) constant-voltage method is: 1～100 volt of reaction potential, 10 seconds～1 hour reaction time, reaction temperature-10～90 degree Celsius.
4. the preparation method of the Ni-based asymmetric ultracapacitor of oxalic acid according to claim 2, is characterized in that the reaction condition of constant flow method is: kinetic current 10 milliamperes～30 peaces, 10 seconds～1 hour reaction time, reaction temperature-10～90 degree Celsius.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104795243A (en) * | 2015-02-04 | 2015-07-22 | 三峡大学 | Asymmetric supercapacitor and preparation method thereof |
| CN109727784A (en) * | 2017-10-27 | 2019-05-07 | 北京碳阳科技有限公司 | Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor |
| CN112133574A (en) * | 2020-11-09 | 2020-12-25 | 湖南科技大学 | Preparation method of foamed nickel @ nickel micro-nanorod array electrode |
| CN114334485A (en) * | 2022-01-24 | 2022-04-12 | 齐鲁工业大学 | Nickel oxalate composite fibrous nickel hydroxide supercapacitor electrode material and preparation method thereof |
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| CN1054104A (en) * | 1991-03-01 | 1991-08-28 | 许昌师范专科学校 | Alternating current electrolysis prepares the method for nickel salt |
| CN2541938Y (en) * | 2002-04-25 | 2003-03-26 | 上海奥威科技开发有限公司 | Super capacitor of vehicle power mains |
| CN2615840Y (en) * | 2003-04-11 | 2004-05-12 | 江苏双登电源有限公司 | Electrochemical super capacitor |
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2013
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| CN1054104A (en) * | 1991-03-01 | 1991-08-28 | 许昌师范专科学校 | Alternating current electrolysis prepares the method for nickel salt |
| CN2541938Y (en) * | 2002-04-25 | 2003-03-26 | 上海奥威科技开发有限公司 | Super capacitor of vehicle power mains |
| CN2615840Y (en) * | 2003-04-11 | 2004-05-12 | 江苏双登电源有限公司 | Electrochemical super capacitor |
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| INSOO JUNG等: "Nickel oxalate nanostructures for supercapacitors", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104795243A (en) * | 2015-02-04 | 2015-07-22 | 三峡大学 | Asymmetric supercapacitor and preparation method thereof |
| CN104795243B (en) * | 2015-02-04 | 2017-09-22 | 三峡大学 | A kind of Asymmetric Supercapacitor and preparation method thereof |
| CN109727784A (en) * | 2017-10-27 | 2019-05-07 | 北京碳阳科技有限公司 | Lithium titanate/carbon material compound, negative electrode material, negative electrode tab and hybrid super capacitor |
| CN112133574A (en) * | 2020-11-09 | 2020-12-25 | 湖南科技大学 | Preparation method of foamed nickel @ nickel micro-nanorod array electrode |
| CN114334485A (en) * | 2022-01-24 | 2022-04-12 | 齐鲁工业大学 | Nickel oxalate composite fibrous nickel hydroxide supercapacitor electrode material and preparation method thereof |
| CN114334485B (en) * | 2022-01-24 | 2023-06-16 | 齐鲁工业大学 | Nickel oxalate composite fibrous nickel hydroxide supercapacitor electrode material and preparation method thereof |
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