CN102664103B - Zinc cobaltate nanorod/foam nickel composite electrode, preparation method thereof and application thereof - Google Patents
Zinc cobaltate nanorod/foam nickel composite electrode, preparation method thereof and application thereof Download PDFInfo
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- CN102664103B CN102664103B CN201210092670.1A CN201210092670A CN102664103B CN 102664103 B CN102664103 B CN 102664103B CN 201210092670 A CN201210092670 A CN 201210092670A CN 102664103 B CN102664103 B CN 102664103B
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Abstract
The invention provides a zinc cobaltate nanorod /foam nickel composite electrode, a preparation method thereof and application thereof. According to the method, a foam nickel plate is immersed in a mixed solution of zinc nitrate and cobalt nitrate, heating and heat preservation are carried out in order, an oxalic acid solution is added dropwise, reaction is carried out until the foam nickel grows a nanostructured precursor, the foam nickel is removed, and cleaning, drying and calcining are carried out in order to obtain the zinc cobaltate nanorod /foam nickel composite electrode. The composite electrode has properties of one-dimensional zinc cobaltate nano material with a large specific surface area and porous foam nickel, a contact area with an electrolyte is effectively increased, the electrode material is more fully involved in an electrochemical reaction, the composite electrode obtained through the reaction has a good electrochemical property and is applied in a super capacitor, the performance of a present capacitor is greatly raised, production process is simple, and the electrode is easy to be applied to the actual mass production.
Description
Technical field
The invention belongs to energy storage of new generation field, particularly a kind of cobalt acid zinc nanometer rods/nickel foam composite construction high power capacity ultracapacitor.
Background technology
Along with the aspects such as communication, electronic equipment, auto industry and space technology develop rapidly, international energy problem in short supply has become increasingly conspicuous, and each state is all in the R and D that step up new forms of energy.In energy storage of new generation field, ultracapacitor and lithium ion battery are indispensable parts, be widely used in rapidly the fields such as mobile phone, notebook computer and military equipment, larger development space will be brought in the electric automobile field of expanding day to ultracapacitor.Compare lithium ion battery, ultracapacitor has huge advantage and the outstanding characteristic of the incomparable power aspect of other energy-storage travelling wave tubes.Although ultracapacitor has higher power density, but be not difficult under study for action to find that the capacitance of ultracapacitor in high power situation and energy density are extremely low, its reason is that this body structure of electrode is single, conductivity, the contact of metal collector and material are poor, in charge and discharge process, due to electrode is destroyed and causes that more greatly surface area is less than normal etc., this restricts it is greatly having larger development on electric automobile from now on.
Summary of the invention
The object of the present invention is to provide a kind of cobalt acid zinc nanometer rods/nickel foam combination electrode, there is the one dimension cobalt acid zinc nano material of bigger serface and the characteristic of loose porous nickel foam simultaneously, can effectively increase the contact area with electrolyte, electrode material is participated in the middle of electrochemical reaction more fully, make material have good chemical property, and there is good flexibility, adapt to the following demand for flexible foldable battery.
Another object of the present invention is to provide the method for the above-mentioned cobalt acid of preparation zinc nanometer rods/nickel foam combination electrode.
The 3rd object of the present invention is to provide the application of above-mentioned cobalt acid zinc nanometer rods/nickel foam combination electrode at ultracapacitor.
A kind of cobalt acid zinc nanometer rods/nickel foam combination electrode, on nickel foam sheet, growth has cobalt acid zinc nanometer rods.
A kind of method of preparing cobalt acid zinc nanometer rods/nickel foam combination electrode, be specially: nickel foam sheet is immersed in the mixed solution of zinc nitrate and cobalt nitrate, insulation after being heated to 80 °-150 ℃, drip oxalic acid solution, reaction is until grow nanostructure presoma in nickel foam, taking-up nickel foam, cleans successively, dries and calcining obtains cobalt acid zinc nanometer rods/nickel foam combination electrode.
Further, the mass concentration of described zinc nitrate and cobalt nitrate is respectively 0.008～0.034mol/L and 0.017～0.066mol/L;
Further, adopt the heating of back flow reaction stove;
Further, insulation 1-2 hour;
Further, at 300～500 ℃, annealing is calcined 2 hours.
The application of cobalt acid zinc nanometer rods/nickel foam combination electrode in ultracapacitor, sets it as the work electrode of ultracapacitor.
The present invention has following beneficial effect:
1. the nickel foam that the present invention adopts good conductivity and has loose porous unique texture is as substrate, at surperficial direct growth cobalt acid zinc nano material, be conducive to so save very much the conductive agent and the binder material that in traditional electrode, use, energy-conserving and environment-protective, have also avoided the process of loaded down with trivial details making electrode slice.Because active material is to produce in nickel foam, so material and substrate contact are very good, be convenient to strengthen electric transmission, be conducive to the cycle performance of ultracapacitor.The multistage composite structure of this novelty has very high practical value.
2. made composite construction has the one dimension cobalt acid zinc nano material of bigger serface and the characteristic of loose porous nickel foam simultaneously, can effectively increase the contact area with electrolyte, electrode material is participated in the middle of electrochemical reaction more fully, make material have good chemical property.
3. the combination electrode making has good flexibility, can adapt to the following demand for flexible foldable battery;
4. the applied ultracapacitor of cobalt acid zinc nanometer rods/nickel foam combination electrode of the present invention is carried out to performance test, after 1000 charge and discharge cycles, capacitance still remains the more than 97% of initial value, shows the cycle life that this ultracapacitor is good.Under the high current density of 20A/g discharges and recharges, this ultracapacitor has up to more than 1000 specific capacitances, adapts to high-power application completely;
5. manufacturing process is simple, and raw material is cheap, only needs the annealing process that the simple circumfluence method of employing and temperature are lower, and equipment requirement and cost are all lower, is suitable for large-scale promotion and produces.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope diagram of pure foam nickel;
Fig. 2 is the scanning electron microscope diagram of the long nickel foam composite construction that has cobalt acid zinc nanometer rods;
Fig. 3 is the scanning electron microscope diagram that the length of amplification has the nickel foam composite construction of cobalt acid zinc nanometer rods;
Fig. 4 is ultracapacitor cycle performance test result figure.
Fig. 5 is ultracapacitor high rate performance test result figure.
Fig. 6 is super capacitor energy density and power density test result figure.
Embodiment
First the present invention makes the long nickel foam that has zinc cobalt oxygen presoma by circumfluence method, anneals afterwards by Muffle furnace again, and presoma is fully oxidized, and makes the long nickel foam that has zinc cobalt oxygen club shaped structure.
Below in conjunction with specific embodiment, technical scheme of the present invention is further described:
Embodiment 1:
1. at normal temperatures, by abundant stirring, zinc nitrate and cobalt nitrate are dissolved in deionized water with the concentration of 0.017mol/L and 0.033mol/L simultaneously, make solution A, and 3～4 nickel foam sheets (as shown in Figure 1) that sheared are immersed in this solution;
2. at normal temperatures, by abundant stirring, oxalic acid is dissolved in deionized water with the concentration of 0.3mol/L, makes solution B; (medicine of use is direct purchase, and the volume ratio of solution A, B is 3: 2)
3. solution A and nickel foam are added in there-necked flask, use the heating of back flow reaction stove until temperature stabilization, at 80 ℃, stirs with Reasonable Speed simultaneously;
4. the oxalic acid solution that is 0.2mol/L by concentration drips and enters in flask, and reacts 2 hours at 80 ℃; Oxalic acid solution object is acid for making reaction solution, and zinc nitrate fully reacts under sour environment with cobalt nitrate, at nickel foam sheet, grows nanostructure presoma.
5. take out nickel sheet, after clean dry, put into Muffle furnace and calcine.At 300 ℃, anneal 120 minutes.Naturally the cooling product (as shown in Figures 2 and 3) that obtains afterwards.
Embodiment 2:
1. at normal temperatures, by abundant stirring, zinc nitrate and cobalt nitrate are dissolved in deionized water with the concentration of 0.008mol/L and 0.017mol/L simultaneously, make solution A, and 3～4 nickel foam sheets that sheared are immersed in this solution;
2. at normal temperatures, by abundant stirring, oxalic acid is dissolved in deionized water with the concentration of 0.3mol/L, makes solution B; (medicine of use is direct purchase, and the volume ratio of solution A, B is 3: 2)
3. solution A and nickel foam are added in there-necked flask, use the heating of back flow reaction stove until temperature stabilization, at 120 ℃, stirs with Reasonable Speed simultaneously;
4. the oxalic acid solution that is 0.2mol/L by concentration drips and enters in flask, and reacts 2 hours at 120 ℃; Oxalic acid solution object is acid for making reaction solution, and zinc nitrate fully reacts under sour environment with cobalt nitrate, at nickel foam sheet, grows nanostructure presoma.
5. take out nickel sheet, after clean dry, put into Muffle furnace and calcine.At 300 ℃, anneal 120 minutes.Naturally the cooling product that obtains afterwards.
Embodiment 3:
1. at normal temperatures, by abundant stirring, zinc nitrate and cobalt nitrate are dissolved in deionized water with the concentration of 0.034mol/L and 0.066mol/L simultaneously, make solution A, and 3～4 nickel foam sheets that sheared are immersed in this solution;
2. at normal temperatures, by abundant stirring, oxalic acid is dissolved in deionized water with the concentration of 0.3mol/L, makes solution B; (medicine of use is direct purchase, and the volume ratio of solution A, B is 3: 2)
3. solution A and nickel foam are added in there-necked flask, use the heating of back flow reaction stove until temperature stabilization, at 150 ℃, stirs with Reasonable Speed simultaneously;
4. the oxalic acid solution that is 0.2mol/L by concentration drips and enters in flask, and reacts 2 hours at 150 ℃; Oxalic acid solution object is acid for making reaction solution, and zinc nitrate fully reacts under sour environment with cobalt nitrate, at nickel foam sheet, grows nanostructure presoma.
5. take out nickel sheet, after clean dry, put into Muffle furnace and calcine.At 300 ℃, anneal 120 minutes.Naturally the cooling product that obtains afterwards.
Embodiment 4:
1. obtain solution process reference example in 1. 1., 2. step, but oxalic acid solution concentration is increased to 0.5mol/L;
2. solution A and nickel foam are added in there-necked flask, use the heating of back flow reaction stove until temperature stabilization, at 100 ℃, stirs with Reasonable Speed simultaneously;
3. oxalic acid solution is dripped and entered in flask, and react 1 hour at 100 ℃;
4. calcining manners is with 1. identical.
This method, owing to having improved the temperature of back flow reaction, can complete reaction in shorter time, but higher temperature has certain influence to the pattern of zinc cobalt oxide nano rod.And because oxalic acid is to guarantee excessively in reaction, therefore change in concentration within the specific limits can not affect reaction result.
Embodiment 5:
1. 4. 3. 2. 1. reaction raw materials preparation and back flow reaction process and embodiment walk in 1. identical.
2. the nickel foam sheet making is placed on to calcination in Muffle furnace, with embodiment 1. in compared with, the temperature of calcination is risen to 500 ℃, annealing time is also made as 120 minutes.Naturally the cooling product that obtains afterwards.
This example and embodiment 1. compared with, because calcination time extends, temperature improves, thus the degree of crystallinity of zinc cobalt oxide nano rod increase to some extent, and also more tight with the combination of nickel foam substrate, but the pattern of small part nanometer rods can be damaged.
Obtain after cobalt acid zinc nanometer rods/nickel foam combination electrode, the work electrode of the present invention using kind electrode as new structure forms three electrode super capacitor test systems together with conventional reference electrode (platinum electrode), reference electrode (mercury/mercury oxide).And adopt the potassium hydroxide solution of 1 mole every liter as electrolyte.The results of property of the ultracapacitor obtaining after test is illustrated in the middle of accompanying drawing 4,5,6.As can be seen from Figure 4, this kind of cobalt acid zinc nanometer rods/nickel foam combination electrode circulates and 1000 times after, still maintains the capacity up to 1200F/g under the electric current of 2A/g, this be existing super capacitor material inaccessiable.And in high electric current (6A/g) charge-discharge test, find that kind electrode can also remain on the high-capacitance of 1000F/g, the cyclical stability of visible cobalt acid zinc nanometer rods/nickel foam combination electrode is given prominence to very much, has guaranteed useful life.Fig. 5 has illustrated the increase along with charging current, the specific capacity of ultracapacitor keeps a metastable scope substantially, this highlights the very good high magnification character of cobalt acid zinc nanometer rods/nickel foam combination electrode, this be after the characteristic that needs especially of batteries of electric automobile.Fig. 6 has shown that this kind of capacitor has up to the energy density of 31Wh/kg and the power density of 20kW/kg.
The present invention is not only confined to above-mentioned embodiment; persons skilled in the art are according to content disclosed by the invention; can adopt other multiple embodiment to implement the present invention; therefore; every employing project organization of the present invention and thinking; do some simple designs that change or change, all fall into the scope of protection of the invention.
Claims (3)
1. prepare the method for cobalt acid zinc nanometer rods/nickel foam combination electrode for one kind, be specially: nickel foam sheet is immersed in the mixed solution of zinc nitrate and cobalt nitrate, insulation after being heated to 80 °～100 ℃, drip oxalic acid solution, reaction is until grow nanostructure presoma in nickel foam, taking-up nickel foam, cleans successively, dries and calcining obtains cobalt acid zinc nanometer rods/nickel foam combination electrode; The mass concentration of described zinc nitrate and cobalt nitrate is respectively 0.008～0.034mol/L and 0.017～0.066mol/L.
2. the method for preparing cobalt acid zinc nanometer rods/nickel foam combination electrode according to claim 1, is characterized in that, the concentration of described zinc nitrate and cobalt nitrate is respectively 0.017～0.034mol/L and 0.033～0.066mol/L.
3. the method for preparing cobalt acid zinc nanometer rods/nickel foam combination electrode according to claim 2, is characterized in that insulation 1-2 hour.
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| CN103440998B (en) * | 2013-08-21 | 2016-05-04 | 吉林大学 | A kind of cobalt acid zinc nanometer sheet array/nickel foam combination electrode, preparation method and application thereof |
| CN103956483B (en) * | 2014-04-30 | 2016-01-13 | 新疆维吾尔自治区产品质量监督检验研究院 | The preparation method and application of cobalt acid zinc/nickel oxide core-shell nano linear array |
| CN104310492B (en) * | 2014-09-29 | 2016-03-30 | 安徽工业大学 | A kind of neodymium cobalt/cobalt oxide nanometer rod and preparation method thereof |
| CN104402066B (en) * | 2014-09-29 | 2016-05-11 | 安徽工业大学 | A kind of terbium cobalt/cobalt oxide nanometer rods and preparation method thereof |
| CN104310493B (en) * | 2014-09-29 | 2016-03-30 | 安徽工业大学 | A kind of dysprosium cobalt/cobalt oxide nanometer rod and preparation method thereof |
| CN105244192A (en) * | 2015-10-27 | 2016-01-13 | 渤海大学 | Magnesium cobaltite porous nanowire array/ nickel foam composite electrode material preparation method |
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| CN105355467A (en) * | 2015-11-27 | 2016-02-24 | 渤海大学 | Preparation method of magnesium cobaltate porous micro-rod/ foamed nickel combined electrode material |
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| CN105895388A (en) * | 2016-06-18 | 2016-08-24 | 合肥松雷信息科技有限公司 | Preparation method for three-dimensional porous sheet-shaped zinc cobaltate nanomaterial |
| CN106340403A (en) * | 2016-09-30 | 2017-01-18 | 江苏大学 | Preparation method and purpose of zinc cobaltate nano wire or nanometer band electrode material |
| CN107032414B (en) * | 2017-03-13 | 2019-04-23 | 中山大学 | A kind of preparation method of flexibility cobalt acid zinc nano-material |
| CN107275105B (en) * | 2017-08-04 | 2019-01-15 | 南京理工大学 | Electrode material for super capacitor and preparation method thereof |
| CN109599564B (en) * | 2018-11-27 | 2022-09-06 | 东华大学 | Nickel cobaltate array self-supporting large-area air electrode and preparation and application thereof |
| CN109850955B (en) * | 2019-03-19 | 2021-10-12 | 合肥国轩高科动力能源有限公司 | Negative electrode material ZnCo of lithium ion battery2O4Method for preparing nano-rod |
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| CN101661840B (en) * | 2009-07-23 | 2011-02-16 | 武汉大学 | Preparation method of super capacitor |
| CN102142318B (en) * | 2011-03-17 | 2012-12-19 | 上海工程技术大学 | Ordered mesoporous carbon/MnO2 nano composite electrode material and preparation method thereof |
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