CN104361996A - Preparation method for directly generating manganese dioxide on surface of substrate - Google Patents
Preparation method for directly generating manganese dioxide on surface of substrate Download PDFInfo
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- CN104361996A CN104361996A CN201410593959.0A CN201410593959A CN104361996A CN 104361996 A CN104361996 A CN 104361996A CN 201410593959 A CN201410593959 A CN 201410593959A CN 104361996 A CN104361996 A CN 104361996A
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- manganese dioxide
- base material
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Abstract
The invention discloses a preparation method for directly generating manganese dioxide on the surface of a substrate. The preparation method includes placing the three-dimensional electrode substrate in a solution containing soluble bivalent manganese salt and oxysalt oxidant; performing chemical deposition through constant-temperature water bath at temperature of 50-80 DEG C. A manganese dioxide electrode prepared by the method through one-time forming does not need a binding agent and has the advantage of low bulb resistance. The formed manganese dioxide is of a three-dimensional structure, thereby being conducive to diffusion of solution ions, and is high in load carrying capacity and electrical conductivity, thereby having the advantages of high capacitance and high circulating performance.
Description
Technical field
The invention belongs to technical field of chemistry, relate to a kind of preparation method directly generating manganese dioxide at substrate surface.
Background technology
For the electrode material of ultracapacitor, not only require that it has height ratio capacity, but also require that low internal resistance is to realize the requirement of big current fast charging and discharging.MnO
2higher in natural abundance, cheap, preparation technology is simple, is the electrode material of development electrochemical capacitor great potential, has become the study hotspot of people in recent years.
The preparation method of manganese oxide electrode mainly contains two kinds, and a kind of method prepares manganese oxide powder by chemistry or Physical, after fully mixing, makes electrode by coating or compressing tablet with binding agent and conductive additive.Another kind method adopts the methods such as collosol and gel, electro-deposition, chemical vapour deposition (CVD), vacuum sputtering directly at metal matrix material Surface Creation sull.MnO
2theoretical capacitance in water system electrolyte can reach more than 1000F/g, but before adopting the electrode prepared of kind method due to the utilance of manganese oxide low, be combined loosely with matrix, contact resistance is large, thus the actual capacitance produced will well below theoretical value, and the electrode such as prepared with hydrated manganese oxide is only 100 ~ 200F/g at the ratio capacitance of salting liquid.Adopt a kind of rear method to be deposited directly to the surperficial manganese oxide membrane electrode capacitance obtained of metal matrix material and can reach about 700F/g, but be only limitted to the very thin layers of material that loading is lower, although thin layer manganese dioxide better performances, but because loading is little, volume and capacity ratio is too low, is difficult to realize commercial applications.
Summary of the invention
In order to solve problems of the prior art, the invention provides a kind of preparation method directly generating manganese dioxide at substrate surface, by three-dimensional foam electrode matrix being put into the solution containing solubility manganous salt and oxysalt oxidant, carry out chemical deposition at water bath with thermostatic control 50 ~ 80 DEG C, make manganese oxide on three-dimensional framework, directly grow the film forming three-dimensional structure.Owing to not using organic binder bond in electrode preparation, and the electrode formed is three-dimensional structure, and loading is large, thus has that volume resistance is little, capacitance is high, the advantage of good cycle.Its technical scheme is:
Directly generate a preparation method for manganese dioxide at substrate surface, comprise the following steps:
(1) preliminary treatment of base material
Base material is the one in nickel foam, foam copper, foamy carbon, activated carbon fiber; Base material is put into the impurity that 0.1M hydrochloric acid solution removes substrate surface for ultrasonic 60 minutes, after repeatedly cleaning with clear water, put into 60 DEG C of drying box dry for standby;
(2) solution preparation
Preparation is containing manganese oxide predecessor MnCl
2with oxidant NaBrO
3mixed solution, wherein MnCl
2concentration is 0.01 ~ 0.1M, NaBrO
3concentration is 0.4M;
(3) manganese dioxide preparation
In the solution prepare base material immersion step (2) after processing with step (1), heating is reacted in a water bath; Bath temperature is 50 ~ 80 DEG C, and heating time controls at 2 ~ 12h.
Compared with prior art, beneficial effect of the present invention is:
The present invention for presoma with the soluble-salt of manganese, take oxysalt as oxidant, directly generates manganese bioxide electrode material on three-dimensional substrates surface.Manganese dioxide electrode prepared by this technology one-shot forming of employing, without the need to adopting adhesive, has the advantages that volume resistance is little, and the manganese dioxide of formation is three-dimensional structure, is conducive to the diffusion of solion.Loading is large, therefore has that capacitance is high, the advantage of good cycle.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph on the manganese dioxide surface of embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph on the manganese dioxide surface of embodiment 2;
Fig. 3 is the scanning electron microscope (SEM) photograph on the manganese dioxide surface of embodiment 3.
Embodiment
Below in conjunction with the drawings and specific embodiments, technical scheme of the present invention is described further.
Embodiment 1
(1) nickel foam base material is put into the impurity that 0.1M hydrochloric acid solution removes substrate surface for ultrasonic 60 minutes, after repeatedly cleaning with clear water, put into 60 DEG C of drying box dry for standby;
(2) preparation is containing manganese oxide predecessor MnCl
2with oxidant NaBrO
3mixed solution, wherein MnCl
2concentration is 0.02M, NaBrO
3concentration is 0.4M;
(3) immerse in step (2) solution prepared with the base material after step (1) process, heating is reacted in a water bath.Bath temperature is 60 DEG C, and heating time controls at 10h.
Prepared manganese dioxide three-dimensional electrode material as shown in Figure 1.
Embodiment 2
(1) nickel foam base material is put into the impurity that 0.1M hydrochloric acid solution removes substrate surface for ultrasonic 60 minutes, after repeatedly cleaning with clear water, put into 60 DEG C of drying box dry for standby;
(2) preparation is containing manganese oxide predecessor MnCl
2with oxidant NaBrO
3mixed solution, wherein MnCl
2concentration is 0.04M, NaBrO
3concentration is 0.4M.
(3) immerse in step (2) solution prepared with the base material after step (1) process, heating is reacted in a water bath.Bath temperature is 70 DEG C, and heating time controls at 4h.
Prepared manganese dioxide three-dimensional electrode material as shown in Figure 2.
Embodiment 3
(1) nickel foam base material is put into the impurity that 0.1M hydrochloric acid solution removes substrate surface for ultrasonic 60 minutes, after repeatedly cleaning with clear water, put into 60 DEG C of drying box dry for standby;
(2) preparation is containing manganese oxide predecessor MnCl
2with oxidant NaBrO
3mixed solution, wherein MnCl
2concentration is 0.08M, NaBrO
3concentration is 0.4M;
(3) immerse in step (2) solution prepared with the base material after step (1) process, heating is reacted in a water bath.Bath temperature is 80 DEG C, and heating time controls at 2h.
Prepared manganese dioxide three-dimensional electrode material as shown in Figure 3.
The above; be only the present invention's preferably embodiment; protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art; in the technical scope that the present invention discloses, the simple transformation of the technical scheme that can obtain apparently or equivalence are replaced and are all fallen within the scope of protection of the present invention.
Claims (1)
1. directly generate a preparation method for manganese dioxide at substrate surface, it is characterized in that, comprise the following steps:
(1) preliminary treatment of base material
Base material is the one in nickel foam, foam copper, foamy carbon, activated carbon fiber; Base material is put into the impurity that 0.1M hydrochloric acid solution removes substrate surface for ultrasonic 60 minutes, after repeatedly cleaning with clear water, put into 60 DEG C of drying box dry for standby;
(2) solution preparation
Preparation is containing manganese oxide predecessor MnCl
2with oxidant NaBrO
3mixed solution, wherein MnCl
2concentration is 0.01 ~ 0.1M, NaBrO
3concentration is 0.4M;
(3) manganese dioxide preparation
In the solution prepare base material immersion step (2) after processing with step (1), heating is reacted in a water bath; Bath temperature is 50 ~ 80 DEG C, and heating time controls at 2 ~ 12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410593959.0A CN104361996A (en) | 2014-10-16 | 2014-10-16 | Preparation method for directly generating manganese dioxide on surface of substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410593959.0A CN104361996A (en) | 2014-10-16 | 2014-10-16 | Preparation method for directly generating manganese dioxide on surface of substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104361996A true CN104361996A (en) | 2015-02-18 |
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ID=52529251
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410593959.0A Pending CN104361996A (en) | 2014-10-16 | 2014-10-16 | Preparation method for directly generating manganese dioxide on surface of substrate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013490A (en) * | 2015-07-03 | 2015-11-04 | 湘潭大学 | Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof |
| CN107093703A (en) * | 2017-04-20 | 2017-08-25 | 陕西科技大学 | A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole |
| CN107275568A (en) * | 2017-07-04 | 2017-10-20 | 福州大学 | A kind of ruthenic oxide Quito pore electrod of graphene doping and preparation method thereof |
| CN110600278A (en) * | 2019-08-22 | 2019-12-20 | 江苏大学 | Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110223477A1 (en) * | 2010-03-12 | 2011-09-15 | Nelson Jennifer A | Alkaline battery including lambda-manganese dioxide and method of making thereof |
| CN103825030A (en) * | 2014-02-27 | 2014-05-28 | 浙江大学 | Three-dimensional graphene-based combined electrode, its preparation method and its application |
-
2014
- 2014-10-16 CN CN201410593959.0A patent/CN104361996A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110223477A1 (en) * | 2010-03-12 | 2011-09-15 | Nelson Jennifer A | Alkaline battery including lambda-manganese dioxide and method of making thereof |
| CN103825030A (en) * | 2014-02-27 | 2014-05-28 | 浙江大学 | Three-dimensional graphene-based combined electrode, its preparation method and its application |
Non-Patent Citations (1)
| Title |
|---|
| 刘宗宇: "Mn的氧化物薄膜的制备与表征", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105013490A (en) * | 2015-07-03 | 2015-11-04 | 湘潭大学 | Metal nanoparticle-foamy carbon catalyst, and preparation method and application thereof |
| CN107093703A (en) * | 2017-04-20 | 2017-08-25 | 陕西科技大学 | A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting negative pole |
| CN107093703B (en) * | 2017-04-20 | 2019-07-02 | 陕西科技大学 | A kind of preparation method of manganese dioxide/foam copper sodium-ion battery self-supporting cathode |
| CN107275568A (en) * | 2017-07-04 | 2017-10-20 | 福州大学 | A kind of ruthenic oxide Quito pore electrod of graphene doping and preparation method thereof |
| CN107275568B (en) * | 2017-07-04 | 2019-08-09 | 福州大学 | A kind of ruthenic oxide Quito pore electrod and preparation method thereof of graphene doping |
| CN110600278A (en) * | 2019-08-22 | 2019-12-20 | 江苏大学 | Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof |
| CN110600278B (en) * | 2019-08-22 | 2022-03-22 | 江苏大学 | Pinecone-shaped MnO2Ball/foam carbon composite material and preparation method thereof |
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Application publication date: 20150218 |
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