CN102689929A - Method for preparing ultralong MnO2 nanowire supercapacitor material - Google Patents
Method for preparing ultralong MnO2 nanowire supercapacitor material Download PDFInfo
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- CN102689929A CN102689929A CN2012101930210A CN201210193021A CN102689929A CN 102689929 A CN102689929 A CN 102689929A CN 2012101930210 A CN2012101930210 A CN 2012101930210A CN 201210193021 A CN201210193021 A CN 201210193021A CN 102689929 A CN102689929 A CN 102689929A
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Abstract
The invention relates to a method for preparing an ultralong MnO2 nanowire supercapacitor material, which comprises the following steps that: (1) potassium permanganate is dissolved in water to obtain a KMnO4 precursor solution; (2) the KMnO4 precursor solution is added in a reaction vessel, and then a polyvinylpyrrolidone surfactant is added to be stirred for 5-30 minutes to obtain a reaction mixed solution; (3) the reaction mixed solution is sealed and then treated at a temperature of 140 to 160 DEG C for 5-10 hours; and (4) after the completion of the reaction, the resultant product is naturally cooled to room temperature, and the product is collected, cleaned and dried at a temperature of 60 to 80 DEG C for 3-5 hours to obtain the material. The preparation method provided by the invention has the advantages that the operation is simple, complex equipment is not needed, the cost is low, the obtained ultralong MnO2 nanowires are uniformly distributed, the electrochemical performance is excellent, and the potential of application in supercapacitor and lithium ion battery materials and the like is great. .
Description
Technical field
The invention belongs to the preparation field of super capacitor material, particularly a kind of MnO
2The preparation method of overlong nanowire super capacitor material.
Background technology
The energy is the basic substance of human survival and development, and face of mankind serious energy scarcity at present.The energy saver of research and development energy storage and recovery is one of effective way that solves energy problem.Electrochemical capacitor is as a kind of novel energy-storing device; Have than much bigger energy density of traditional capacitor and the power density more much higher than battery, advantage such as the energy collecting metric density is high, power density is high, have extended cycle life, the duration of charging is short and the storage cycle is long.At aspects such as automobile, electric power, railway, communication, national defence, consumer electronic product huge using value and market potential are arranged, caused domestic and international scientist's extensive interest.As everyone knows, the electrode materials that is widely used in ultracapacitor has porous carbon material, transition metal oxide and conductive polymers (Winter et al, Chem.Rev., 2004,104,4245).
In these materials, the Manganse Dioxide in the transition metal oxide is considered to the most attractive selection, and cost is low because it has, environmental friendliness and superior capacitive property, has caused the extensive concern of vast researcher.The manganese oxide material of present various patterns all is produced, and method is various, for example chemical precipitation method, solid phase method, sol-gel method or the like (Wang et al, J.Power Sources, 2006,153,191-196).Yet the low electronic conductivity of Mn oxide has limited its application aspect the high-performance ultracapacitor.In order to improve desired properties, monodimension nanometer material is goed deep into broad research, and it has high-specific surface area, and therefore the characteristics that electronics and ion diffusion approach are short have higher charge.Existing human combines plurality of step to prepare one dimension manganese oxide material with complicated method, therefore, needs a kind of method simply and easily of development, prepares eco-friendly, as to have excellent properties MnO
2Super capacitor material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of MnO
2The preparation method of overlong nanowire super capacitor material, simple to operate, do not need complex apparatus, with low cost; Prepared overlength MnO
2Nano wire is evenly distributed, and chemical property is excellent.
A kind of MnO of the present invention
2The preparation method of overlong nanowire super capacitor material comprises:
(1) potassium permanganate is soluble in water, obtain KMnO
4Precursor solution is to obtain to be suitable for MnO
2The reaction soln of overlong nanowire growth;
(2) in reaction vessel, add KMnO
4Precursor solution adds the Vinylpyrrolidone polymer tensio-active agent again, stirs 5-30 minute, obtains being suitable for MnO
2The reaction mixture of overlong nanowire growth;
(3) with above-mentioned reaction mixture sealing, then in 140-160 ℃ of processing 5-10 hour, to obtain MnO
2The hydrothermal condition of overlong nanowire growth;
(4) after reaction is accomplished, naturally cool to room temperature, collect product, clean the back, promptly obtain MnO in 60-80 ℃ of dry 3-5 hour
2The overlong nanowire super capacitor material.
KMnO in the step (2)
4Precursor solution accounts for reaction vessel volumetrical 60-80%.
Described reaction vessel is the tetrafluoroethylene reaction kettle.
KMnO in the reaction mixture described in the step (2)
4With the mol ratio of Vinylpyrrolidone polymer PVP be 40:1-5.
PVP is dissolved in the potassium permanganate precursor solution fully in the reaction mixture described in the step (2).
The concentration of potassium permanganate is 0.005-0.02mol/L in the reaction mixture described in the step (2).
Being sealed into described in the step (3) adopted the stainless steel cauldron sealing.
Vinylpyrrolidone polymer tensio-active agent described in the step (3) is PVP-K25, PVP-K30 or PVP-K90.
Cleaning described in the step (4) is for using ethanol, deionized water rinsing each 3-5 time respectively.
MnO described in the step (4)
2Overlong nanowire is the micron order super-long structural, is about 20 ~ 40 μ m, the about 10 ~ 20nm of width.
The MnO of the present invention's preparation
2Nano wire has good electrochemical stability, and circulating does not have capacitance loss 3000 times basically.Because potassium permanganate and Vinylpyrrolidone polymer material price are cheap, the product of hydrothermal preparation need not proceeded to handle, and just can obtain overlength, the excellent material of chemical property.
The present invention passes through simple hydrothermal technique, successful synthetic overlength, the MnO that chemical property is excellent
2Nano wire will be in the technology of preparing of exploring the novel electrode material, screen the electrode materials of even more ideal, high specific capacitance or volume energy density, high charge-discharge power density, improves the performance of electrochemical capacitor, and solution energy scarcity aspect contributes.
The present invention is a raw material with common inorganics and tensio-active agent on the basis on no follow-up use low surface energy material modified product surface, through experiment parameters such as concentration of reactants, time, temperature in the adjusting hydrothermal reaction process, prepares MnO
2Nano wire obtains overlength, the excellent MnO of chemical property that big area is evenly distributed
2Nano wire, and when changing reaction parameter, can change MnO
2The size of nano material and pattern.
Beneficial effect
(1) preparation method of the present invention is simple to operate, does not need complex apparatus, and is with low cost;
(2) prepared overlength MnO
2Nano wire is evenly distributed, and chemical property is excellent, at aspects such as ultracapacitor, lithium ion battery materials application potential is arranged.
Description of drawings
Fig. 1 is the MnO of the present invention's preparation
2The low power ESEM picture of nano wire;
Fig. 2 is the MnO of the present invention's preparation
2The XRD figure sheet of nano wire;
Fig. 3 is the MnO of the present invention's preparation
2The cyclical stability test picture of nano wire;
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
The present invention adopts the hydro-thermal synthetic technology; Through allocating specific reaction soln, the conductive glass substrate level that will pass through cleaning is immersed in reaction kettle inner bag bottom, under the condition of comparatively high temps; Hydro-thermal reaction for some time, preparation overlength, the excellent MnO of chemical property
2Nano wire.
Embodiment 1
Utilize solid potassium permanganate and deionized water to be configured to KMnO
4Red-purple KMnO (0.005mol/L)
4Precursor solution, the KMnO of about 60% volume of in the reaction kettle inner bag of tetrafluoroethylene, packing into
4Precursor solution adds Vinylpyrrolidone polymer tensio-active agent (Vinylpyrrolidone polymer and KMnO
4Mol ratio be 3:40), stirred 10 minutes, then with stainless steel cauldron sealing, place about 140 ℃ baking oven to handle 5 hours; Reaction naturally cools to room temperature after accomplishing, and collects product; Use ethanol, deionized water rinsing each 5 times respectively, 60 ℃, dry 3 hours, obtain MnO
2Overlong nanowire.
Embodiment 2
Utilize solid potassium permanganate and deionized water to be configured to KMnO
4Red-purple KMnO (0.010mol/L)
4Precursor solution, the KMnO of about 70% volume of in the reaction kettle inner bag of tetrafluoroethylene, packing into
4Precursor solution adds a certain amount of Vinylpyrrolidone polymer tensio-active agent (Vinylpyrrolidone polymer and KMnO
4Mol ratio be 4:40), stirred 10 minutes, then with stainless steel cauldron sealing, place about 150 ℃ baking oven to handle 6 hours; Reaction naturally cools to room temperature after accomplishing, and collects product; Use ethanol, deionized water rinsing each 4 times respectively, 70 ℃, dry 4 hours, obtain MnO
2Overlong nanowire.
Embodiment 3
Utilize solid potassium permanganate and deionized water to be configured to KMnO
4Red-purple KMnO (0.015mol/L)
4Precursor solution, the KMnO of about 70% volume of in the reaction kettle inner bag of tetrafluoroethylene, packing into
4Precursor solution adds a certain amount of Vinylpyrrolidone polymer tensio-active agent (Vinylpyrrolidone polymer and KMnO
4Mol ratio be 2:40), stirred 10 minutes, then with stainless steel cauldron sealing, place about 150 ℃ baking oven to handle 7 hours; Reaction naturally cools to room temperature after accomplishing, and collects product; Use ethanol, deionized water rinsing each 3 times respectively, 70 ℃, dry 4 hours, obtain MnO
2Overlong nanowire.
Embodiment 4
Utilize solid potassium permanganate and deionized water to be configured to KMnO
4Red-purple KMnO (0.02mol/L)
4Precursor solution, the KMnO of about 80% volume of in the reaction kettle inner bag of tetrafluoroethylene, packing into
4Precursor solution adds a certain amount of Vinylpyrrolidone polymer tensio-active agent (Vinylpyrrolidone polymer and KMnO
4Mol ratio be 3:40), stirred 10 minutes, then with stainless steel cauldron sealing, place about 160 ℃ baking oven to handle 8 hours; Reaction naturally cools to room temperature after accomplishing, and collects product; Use ethanol, deionized water rinsing each 3 times respectively, 80 ℃, dry 5 hours, obtain MnO
2Overlong nanowire.
Claims (9)
1. MnO
2The preparation method of overlong nanowire super capacitor material comprises:
(1) potassium permanganate is soluble in water, obtain KMnO
4Precursor solution;
(2) in reaction vessel, add above-mentioned KMnO
4Precursor solution adds the tensio-active agent Vinylpyrrolidone polymer again, stirs 5-30 minute, obtains reaction mixture;
(3) with above-mentioned reaction mixture sealing, handled 5-10 hour in 140-160 ℃ then;
(4) after reaction is accomplished, naturally cool to room temperature, collect product, clean the back, promptly get in 60-80 ℃ of dry 3-5 hour.
2. a kind of MnO according to claim 1
2The preparation method of overlong nanowire super capacitor material is characterized in that: KMnO in the step (2)
4Precursor solution accounts for reaction vessel volumetrical 60-80%.
3. a kind of MnO according to claim 1 and 2
2The preparation method of overlong nanowire super capacitor material is characterized in that: described reaction vessel is the tetrafluoroethylene reaction kettle.
4. a kind of MnO according to claim 1
2The preparation method of overlong nanowire super capacitor material is characterized in that: KMnO in the reaction mixture described in the step (2)
4With the mol ratio of Vinylpyrrolidone polymer be 40:1-5.
5. a kind of MnO according to claim 1
2The preparation method of overlong nanowire super capacitor material is characterized in that: KMnO in the reaction mixture described in the step (2)
4Concentration be 0.005-0.02mol/L.
6. a kind of MnO according to claim 1
2The preparation method of overlong nanowire super capacitor material is characterized in that: being sealed into described in the step (3) adopted the stainless steel cauldron sealing.
7. a kind of MnO according to claim 1
2The preparation method of overlong nanowire super capacitor material is characterized in that: the Vinylpyrrolidone polymer described in the step (3) is PVP-K25, PVP-K30 or PVP-K90.
8. a kind of MnO according to claim 1
2The preparation method of overlong nanowire super capacitor material is characterized in that: the cleaning described in the step (4) is for using ethanol, deionized water rinsing each 3-5 time respectively.
9. a kind of MnO according to claim 1
2The preparation method of overlong nanowire super capacitor material is characterized in that: the MnO described in the step (4)
2Overlong nanowire is the micron order super-long structural, long 20 ~ 40 μ m, wide 10 ~ 20nm.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682303A (en) * | 2013-11-11 | 2014-03-26 | 江苏华东锂电技术研究院有限公司 | Lithium ion battery, active material of negative electrode thereof, and preparation method of active material |
| CN104409220A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method of manganese dioxide nanowire material and application of manganese dioxide nanowire material as electrode material of supercapacitor |
| CN104628039A (en) * | 2015-02-06 | 2015-05-20 | 南京工业大学 | Controllable preparation method of alpha-manganese dioxide nanowire |
| CN105097302A (en) * | 2015-09-15 | 2015-11-25 | 江苏苏通碳纤维有限公司 | Activated carbon fibers for supercapacitor and preparation method therefor |
| CN106082345A (en) * | 2016-06-14 | 2016-11-09 | 中山大学 | A kind of preparation method of nano-manganese dioxide line |
| CN106745285A (en) * | 2017-03-01 | 2017-05-31 | 哈尔滨工业大学 | A kind of α MnO2The preparation method of nano wire |
| CN107540023A (en) * | 2017-10-30 | 2018-01-05 | 重庆大学 | A kind of overlength manganese dioxide nanowire material and preparation method thereof |
| CN107537474A (en) * | 2017-10-19 | 2018-01-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of support type ozone catalyst and products thereof and application |
| CN108735524A (en) * | 2018-03-30 | 2018-11-02 | 广东工业大学 | A kind of dilute flexible super capacitor of graphite of the self-healing of high elongation deformation and its preparation method and application |
| CN110061209A (en) * | 2019-04-03 | 2019-07-26 | 合肥国轩高科动力能源有限公司 | A kind of MnO2@V2O5Core-shell nano material and preparation method thereof, application |
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| CN1789145A (en) * | 2005-11-07 | 2006-06-21 | 山东师范大学 | Method for synthesizing nano-structure of bunchy manganese dioxide |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682303A (en) * | 2013-11-11 | 2014-03-26 | 江苏华东锂电技术研究院有限公司 | Lithium ion battery, active material of negative electrode thereof, and preparation method of active material |
| CN104409220A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method of manganese dioxide nanowire material and application of manganese dioxide nanowire material as electrode material of supercapacitor |
| CN104409220B (en) * | 2014-11-28 | 2017-05-17 | 西北师范大学 | Preparation method of manganese dioxide nanowire material and application of manganese dioxide nanowire material as electrode material of supercapacitor |
| CN104628039A (en) * | 2015-02-06 | 2015-05-20 | 南京工业大学 | Controllable preparation method of alpha-manganese dioxide nanowire |
| CN105097302A (en) * | 2015-09-15 | 2015-11-25 | 江苏苏通碳纤维有限公司 | Activated carbon fibers for supercapacitor and preparation method therefor |
| CN106082345A (en) * | 2016-06-14 | 2016-11-09 | 中山大学 | A kind of preparation method of nano-manganese dioxide line |
| CN106745285A (en) * | 2017-03-01 | 2017-05-31 | 哈尔滨工业大学 | A kind of α MnO2The preparation method of nano wire |
| CN106745285B (en) * | 2017-03-01 | 2018-07-03 | 哈尔滨工业大学 | A kind of α-MnO2The preparation method of nano wire |
| CN107537474A (en) * | 2017-10-19 | 2018-01-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of support type ozone catalyst and products thereof and application |
| CN107537474B (en) * | 2017-10-19 | 2019-11-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of support type ozone catalyst and products thereof and application |
| CN107540023A (en) * | 2017-10-30 | 2018-01-05 | 重庆大学 | A kind of overlength manganese dioxide nanowire material and preparation method thereof |
| CN107540023B (en) * | 2017-10-30 | 2019-04-26 | 重庆大学 | A kind of overlength manganese dioxide nanowire material and preparation method thereof |
| CN108735524A (en) * | 2018-03-30 | 2018-11-02 | 广东工业大学 | A kind of dilute flexible super capacitor of graphite of the self-healing of high elongation deformation and its preparation method and application |
| CN110061209A (en) * | 2019-04-03 | 2019-07-26 | 合肥国轩高科动力能源有限公司 | A kind of MnO2@V2O5Core-shell nano material and preparation method thereof, application |
| CN110061209B (en) * | 2019-04-03 | 2022-03-04 | 合肥国轩高科动力能源有限公司 | MnO (MnO)2@V2O5Core-shell nano material and preparation method and application thereof |
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Application publication date: 20120926 |