CN109741957A - A kind of Pt/MnO2@carbon nanohorn composite material and preparation method and application - Google Patents
A kind of Pt/MnO2@carbon nanohorn composite material and preparation method and application Download PDFInfo
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- 239000002116 nanohorn Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 12
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000002604 ultrasonography Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 239000003990 capacitor Substances 0.000 abstract description 7
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000115658 Dahlia pinnata Species 0.000 description 1
- 235000012040 Dahlia pinnata Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention discloses a kind of Pt/MnO2@carbon nanohorn composite material and preparation method and application.Method includes the following steps: carbon nanohorn is placed in acid solution by (1), reflux is washed out to neutrality, drying for standby；(2) ethylene glycol is added in through step (1) treated carbon nanohorn, then potassium permanganate is added in ultrasound, flow back；Add K2PtCl6, reflux；(3) washing step (2) products therefrom, is dried overnight, and then anneal in atmosphere of inert gases 2~4h, and Pt/MnO is made2@carbon nanohorn composite material.The Pt/MnO that the present invention is prepared2@carbon nanohorn composite material stability is good, has excellent capacitive property, is a kind of ideal super capacitor material.
Description
Technical field
The invention belongs to electrode fabrication fields, and in particular to a kind of Pt/MnO2@carbon nanohorn composite material and its system
Preparation Method and application.
Background technique
Manganese dioxide has the characteristics that content abundant, cheap, environmental-friendly and toxicity is lesser and manganese oxide exists
Good capacitance characteristic can be presented in neutral electrolyte, theoretical capacity is big, and manganese dioxide active material is in aqueous electrolyte
In energy storage mechnism be mainly by manganese dioxide surface carry out high reversible faraday's redox reaction it is counterfeit to obtain
Capacitance, wherein charge then passes through Mn4+And Mn3+It is mutual conversion and generate.But MnO2Self-conductive rate is lower, causes its poor
Chemical property, and its cyclical stability still needs further to be studied with energy storage mechnism.Carbon material with its lower resistance,
The specific surface area and porosity of good electric conductivity and super large, become MnO2First choice of ideal composite material.
Summary of the invention
For above-mentioned deficiency in the prior art, the present invention provides a kind of Pt/MnO2@carbon nanohorn composite material and its system
Preparation Method and application, can effectively solve that existing electrode material stability is poor, the problem of capacitive property deficiency.
To achieve the above object, the technical solution adopted by the present invention to solve the technical problems is:
A kind of Pt/MnO2The preparation method of@carbon nanohorn composite material, comprising the following steps:
(1) carbon nanohorn is placed in acid solution, in 100~120 DEG C of 8~10h of reflux, is washed out to neutrality, done
It is dry spare；
(2) ethylene glycol is added in through step (1) treated carbon nanohorn, then potassium permanganate is added in ultrasound, ultrasound
20~25min, in 100~120 DEG C of 3~5h of reflux；Add K2PtCl620~30min of ultrasound, in 130~150 DEG C flow back 3~
5h；The carbon nanohorn, potassium permanganate and K2PtCl6Weight ratio be 1~3:2~5:1.5~3；
(3) washing step (2) products therefrom 5~6 times, are dried overnight in 80~100 DEG C, then lazy in 500~600 DEG C
Property atmosphere in anneal 2~4h, be made Pt/MnO2@carbon nanohorn composite material.
Further, acid solution described in step (1) is nitric acid solution.
Further, the detailed process to flow back in step (1) are as follows: in 110 DEG C of reflux 8h.
Further, carbon nanohorn, potassium permanganate and K in step (2)2PtCl6Weight ratio be 1:5:2.
Further, after potassium permanganate being added in step (2), in 100 DEG C of oil baths reflux 3h.
Further, K is added in step (2)2PtCl6, in 135 DEG C of oil baths reflux 3h.
Further, the detailed process washed in step (3) are as follows: use distilled water and dehydrated alcohol washing step (2) respectively
Products therefrom is respectively three times.
The Pt/MnO that the above method is prepared2@carbon nanohorn composite material.
Above-mentioned Pt/MnO2@carbon nanohorn composite material is preparing the application in electrode comprising following steps:
(1) Pt/MnO that will be prepared2@carbon nanohorn composite material crushes, and then mixes with conductive agent and binder,
And suitable dehydrated alcohol is added, it stirs evenly, paste is made；Wherein, Pt/MnO2@carbon nanohorn composite material, conductive agent
Weight ratio with binder is 80:15:5；
(2) with 5~10mg/cm2Coated weight, paste is uniformly coated on specification be 1cm × 1cm nickel foam table
Face, in 80~100 DEG C dry 8~10, then under conditions of 5~8MPa, electrode is prepared in compression moulding.
Further, conductive agent is acetylene black in step (1).
Further, binder is polytetrafluoroethylene (PTFE) in step (1).
The invention has the benefit that
1, the surface SWCNHs after acidification is very clean, and impurity is less, so that Pt/MnO2Can uniformly it disperse in situ
On the surface SWCNHs, SWCNHs Pt/MnO2Nano particle provides quick charge delivering path, and it is compound after
SWCNHs maintains original structure feature, provides free-moving space for electron-transport, helps to improve fake capacitance performance.
2, in the Pt/MnO being prepared2In@SWCNH composite material, SWCNH has huge specific surface area, not only
Electric double layer capacitance can be provided as active material, moreover it is possible to be MnO2Mechanical support and conductive network, while Pt nanometers are provided
Particle also further increases electric conductivity, eventually by with MnO2Synergistic effect greatly improve capacitor, show Pt/MnO2@SWCNH
Composite material has good capacitance characteristic, is a kind of ideal super capacitor material.
3, current density be 1A/g when and voltage range constant current charge-discharge test, Pt/ are carried out under 0 to 0.8V
MnO2@SWCNH, MnO2The shape that the constant current charge-discharge curve of@SWCNH and SWCNH electrode shows isosceles triangle is special
Sign, the specific capacitance of material can be calculated from the discharge time of 3 curves, by the specific capacitance for calculating SWCNH electrode material
Value can reach 77.3F/g, MnO2The specific capacitance of@SWCNH electrode material has reached 242.8F/g, and Pt/MnO2@SWCNH electrode material
The specific capacitance of material has reached 314.5F/g；Show MnO2Capacitive property is greatly improved by synergistic effect with Pt and SWCNH, is one
The ideal super capacitor material of kind.
Detailed description of the invention
The TEM figure that Fig. 1 is the SWCNHs under 200nm enlargement ratio；
The TEM figure that Fig. 2 is the SWCNHs under 20nm enlargement ratio；
Fig. 3 is the Pt/MnO under 100nm enlargement ratio2The TEM of@carbon nanohorn composite material schemes；
Fig. 4 is the Pt/MnO under 20nm enlargement ratio2The TEM of@carbon nanohorn composite material schemes；
Fig. 5 is XPS spectrum figure；Wherein, Fig. 5 A is MnO2@SWCNH and Pt/MnO2The XPS spectrum figure of@SWCNH；Fig. 5 B be
MnO2XPS spectrum figure on@SWCNH after supporting Pt；Fig. 5 C is the XPS spectrum figure with Mn2p characteristic peak；
Fig. 6 is SWCNH, MnO2@SWCNH and Pt/MnO2Perseverance of the@SWCNH composite electrode in the case where current density is 1A/g
Flow charging and discharging curve figure；
Fig. 7 is SWCNH, MnO2@SWCNH and Pt/MnO2@SWCNH composite electrode is in different current densities (1,2,3,5
And 10A/g) under specific capacitance change curve；
Fig. 8 is SWCNHs, MnO2@SWCNHs and Pt/MnO2@SWCNHs composite material current density be 1A/g when, with
The variation diagram of cycle-index specific capacitance.
Specific embodiment
A specific embodiment of the invention is described below, in order to facilitate understanding by those skilled in the art this hair
It is bright, it should be apparent that the present invention is not limited to the ranges of specific embodiment, for those skilled in the art,
As long as various change is in the spirit and scope of the present invention that the attached claims limit and determine, these variations are aobvious and easy
See, all are using the innovation and creation of present inventive concept in the column of protection.
Embodiment 1
A kind of Pt/MnO2The preparation method of@carbon nanohorn composite material, which comprises the following steps:
(1) carbon nanohorn is placed in acid solution, in 110 DEG C of reflux 8h, is then washed with deionized to neutrality, very
Empty drying for standby；
(2) 20mg is weighed through step (1) treated carbon nanohorn, and 40mL ethylene glycol is added, ultrasonic disperse is suspension,
Then 100mg potassium permanganate is added, and after continual ultrasonic 20min, in 100 DEG C of oil baths reflux 3h；Add 40mg K2PtCl6It is super
Sound 20min, then in 135 DEG C of oil baths reflux 3h；
(3) distilled water and dehydrated alcohol washing step (2) products therefrom is used respectively three times, to be dried overnight in 80 DEG C, so respectively
Anneal in 500 DEG C of argon atmosphere 2h afterwards, and Pt/MnO is made2@carbon nanohorn composite material.
Above-mentioned Pt/MnO2@carbon nanohorn composite material is preparing the application in electrode, comprising the following steps:
(1) Pt/MnO that will be prepared2@carbon nanohorn composite material crush, then with acetylene black and polytetrafluoroethylene (PTFE)
Mixing, and suitable dehydrated alcohol is added, it stirs evenly, paste is made；Wherein, Pt/MnO2@carbon nanohorn composite material,
The weight ratio of conductive agent and binder is 80:15:5；
(2) with 5~10mg/cm2Coated weight, paste is uniformly coated on specification be 1cm × 1cm nickel foam table
Face then under conditions of 5MPa, is prepared using mixed pressuring plate method by tablet press machine compression moulding in 80 DEG C of dry 8h
Electrode.
Embodiment 2
A kind of Pt/MnO2The preparation method of@carbon nanohorn composite material, which comprises the following steps:
(1) carbon nanohorn is placed in acid solution, in 100 DEG C of reflux 9h, is then washed with deionized to neutrality, very
Empty drying for standby；
(2) 20mg is weighed through step (1) treated carbon nanohorn, and 40mL ethylene glycol is added, ultrasonic disperse is suspension,
Then 80mg potassium permanganate is added, and after continual ultrasonic 30min, in 120 DEG C of oil baths reflux 3h；Add 60mg K2PtCl6It is super
Sound 20min, then in 130 DEG C of oil baths reflux 3h；
(3) distilled water and dehydrated alcohol washing step (2) products therefrom is used respectively three times, to be dried overnight in 100 DEG C, so respectively
Anneal in 600 DEG C of argon atmosphere 2h afterwards, and Pt/MnO is made2@carbon nanohorn composite material.
Above-mentioned Pt/MnO2@carbon nanohorn composite material is preparing the application in electrode, comprising the following steps:
(1) Pt/MnO that will be prepared2@carbon nanohorn composite material crush, then with acetylene black and polytetrafluoroethylene (PTFE)
Mixing, and suitable dehydrated alcohol is added, it stirs evenly, paste is made；Wherein, Pt/MnO2@carbon nanohorn composite material,
The weight ratio of conductive agent and binder is 80:15:5；
(2) with 5~10mg/cm2Coated weight, paste is uniformly coated on specification be 1cm × 1cm nickel foam table
Face then under conditions of 5MPa, is prepared using mixed pressuring plate method by tablet press machine compression moulding in 80 DEG C of dry 8h
Electrode.
Embodiment 3
A kind of Pt/MnO2The preparation method of@carbon nanohorn composite material, which comprises the following steps:
(1) carbon nanohorn is placed in acid solution, in 110 DEG C of reflux 8h, is then washed with deionized to neutrality, very
Empty drying for standby；
(2) 10mg is weighed through step (1) treated carbon nanohorn, and 40mL ethylene glycol is added, ultrasonic disperse is suspension,
Then 30mg potassium permanganate is added, and after continual ultrasonic 30min, in 110 DEG C of oil baths reflux 3h；Add 15mg K2PtCl6It is super
Sound 20min, then in 150 DEG C of oil baths reflux 5h；
(3) distilled water and dehydrated alcohol washing step (2) products therefrom is used respectively three times, to be dried overnight in 90 DEG C, so respectively
Anneal in 550 DEG C of argon atmosphere 2h afterwards, and Pt/MnO is made2@carbon nanohorn composite material.
Above-mentioned Pt/MnO2@carbon nanohorn composite material is preparing the application in electrode, comprising the following steps:
(1) Pt/MnO that will be prepared2@carbon nanohorn composite material crush, then with acetylene black and polytetrafluoroethylene (PTFE)
Mixing, and suitable dehydrated alcohol is added, it stirs evenly, paste is made；Wherein, Pt/MnO2@carbon nanohorn composite material,
The weight ratio of conductive agent and binder is 80:15:5；
(2) with 5~10mg/cm2Coated weight, paste is uniformly coated on specification be 1cm × 1cm nickel foam table
Face then under conditions of 5MPa, is prepared using mixed pressuring plate method by tablet press machine compression moulding in 80 DEG C of dry 8h
Electrode.
Comparative example
Compared with Example 1, lack K in step (2)2PtCl6, remaining process is same as Example 1, is prepared
MnO2@carbon nanohorn composite material.
Experimental example
One, the SWCNHs to the acidified processing of the embodiment 1 and Pt/MnO being prepared2The shape of@SWCNH composite material
Looks are characterized, and the result is shown in Figure 1~and 4.
Fig. 1 and Fig. 2 is respectively the TEM figure of 200nm and 20nm enlargement ratio SWCNHs, as depicted in figs. 1 and 2, SWCNHs
Be presented the structure of transparence, dahlia shape, evenly dispersed soilless sticking, and it is acidified it is processed after the surface SWCNHs very
Completely, impurity is less, shows that acidified processing is highly effective.
Fig. 3 and Fig. 4 is respectively 100nm and 20nm enlargement ratio Pt/MnO2The TEM of@SWCNH schemes, as shown in Figure 3 and Figure 4,
Pt/MnO2It is uniformly in situ to be dispersed in the surface SWCNHs, SWCNHs Pt/MnO2Nano particle provides quick charge delivering path,
And the SWCNHs after compound maintains original structure feature, provides free-moving space for electron-transport, facilitates
Improve fake capacitance performance.
Two, the Pt/MnO that embodiment 1 and comparative example are prepared2@SWCNH and MnO2@SWCNH carries out x-ray photoelectron
Energy spectrum analysis, the result is shown in Fig. 5.
As shown in Figure 5A, in MnO2In the XPS spectrum figure of@SWCNH, there is C1s, O1s, Mn2p and Mn3p characteristic peak.
As shown in Figure 5 B, in Pt/MnO2In the XPS spectrum figure of@SWCNH, by MnO2On@SWCNH after supporting Pt, out
Showed Pt4f characteristic peak, in the high-resolution XPS spectrum figure of Pt4f, display Pt4f is split into two peaks, respectively in 71.36eV and
74.68eV place corresponds to Pt4f7/2And Pt4f5/2, indicate that Pt nanoparticle is successfully prepared MnO2In@SWCNH compound.
As shown in Figure 5 C, in the high-resolution XPS spectrum figure of Mn2p, Mn2p is shown3/2And Mn2p1/2Respectively in 641.91eV and
Respectively there is a peak at 653.60eV, is 11.69eV, the data and documents and materials of detection by calculating the spacing between two peaks of discovery
Middle result is consistent；Show successfully to prepare Pt/MnO2@SWCNH compound, and there is good crystal form.
Three, the Pt/MnO that embodiment 1 is prepared using constant current charge-discharge technology2@SWCNH composite material, SWCNH with
And the MnO that comparative example is prepared2@SWCNH is detected, and the result is shown in Fig. 6.
As shown in fig. 6, current density be 1A/g when and voltage range constant current charge-discharge is carried out under 0 to 0.8V
Test, Pt/MnO2@SWCNH, MnO2The constant current charge-discharge curve of@SWCNH and SWCNH electrode shows isosceles triangle
Shape feature, then further according to the specific capacitance calculation formula of electrode material:
Wherein, I/m is current density；⊿ t is discharge time；⊿ V is potential difference；
The specific capacitance of material can be calculated from the discharge time of 3 curves, by the ratio for calculating SWCNH electrode material
Capacitance can reach 77.3F/g, MnO2The specific capacitance of@SWCNH electrode material has reached 242.8F/g, and Pt/MnO2@SWCNH electricity
The specific capacitance of pole material has reached 314.5F/g.
Wherein SWCNH has huge specific surface area, and SWCNH serves not only as active material and provides electric double layer capacitance, simultaneously
For MnO2There is provided mechanical support and conductive network, while Pt nano particle also further increases electric conductivity, eventually by with MnO2
Synergistic effect greatly improve capacitor, testing result shows Pt/MnO2@SWCNH combination electrode has good capacitance characteristic, is
A kind of ideal super capacitor material.MnO2Capacitive property is greatly improved by synergistic effect with Pt and SWCNH.Testing result
Show Pt/MnO2@SWCNH combination electrode has good capacitance characteristic, is a kind of ideal super capacitor material.
Four, the Pt/MnO that embodiment 1 is prepared under 1,2,3,5 and 10A/g current density respectively2@SWCNH is compound
The MnO that material, SWCNH and comparative example are prepared2@SWCNH carries out constant current charge-discharge, and the result is shown in Fig. 7；As shown in fig. 7,
Pt/MnO2@SWCNH composite electrode still has good capacitive property and high specific capacitance under high current density, is in
Existing outstanding high rate performance, therefore Pt/MnO2@SWCNH compound is the ideal electrode material of supercapacitor.
Five, the Pt/MnO that embodiment 1 is prepared2What@SWCNH composite material, SWCNH and comparative example were prepared
MnO2@SWCNH carries out cyclical stability detection, and the result is shown in Fig. 8.
As shown in figure 8, under conditions of current density is 1A/g, by SWCNHs, MnO2@SWCNHs and Pt/MnO2@
SWCNHs composite electrode carries out the constant current charge-discharge loop test in 1000 periods.After 1000 cycle periods,
SWCNHs is reduced to 69.68F/g by initial specific capacitance 77.3F/g, and specific capacitance still keeps 90.14%, MnO of initial capacity2@
SWCNHs composite electrode is reduced to 209.6F/g by initial specific capacitance 242.8F/g, and specific capacitance still keeps initial capacity
86.33%, Pt/MnO2@SWCNHs composite electrode is then reduced to 273.28F/g, specific capacitance by initial specific capacitance 314.5F/g
The 86.89% of initial capacity is still kept, excellent cyclical stability is shown.The mechanism for improving cyclical stability is SWCNHs
Contained huge specific surface area can be with MnO2Carry out it is compound, be MnO2Mechanical conductive network bracket is provided, its conduction is improved
Property, the migration rate of electronics is accelerated, and the addition of Pt nano particle particle further improves its electric conductivity, therefore greatly mention
The high cyclical stability of composite material, passes through and calculates Pt/MnO2The energy density of@SWCNHs composite electrode is 27.96Wh/
Kg, power density 410.78W/kg, the results showed that Pt/MnO2@SWCNHs composite electrode has good cycle life, should
Material can be used to production supercapacitor.
In conclusion the Pt/MnO that the method for the present invention is prepared2In@SWCNHs composite material, Pt/MnO2Nano particle
It is uniformly dispersed on SWCNHs, the high-specific surface area of SWCNHs not only provides electric double layer capacitance, is also MnO2Nano particle mentions
For mechanical support and conductive network is formed, improves MnO2Electric conductivity, alleviate MnO2Volume in nano particle charge and discharge process
Effect, while Pt further increases electric conductivity, improves its fake capacitance performance, improves high rate performance and cyclical stability, shows it
With good electro-chemical activity, it is suitable as the electrode material of supercapacitor；This is the Pt/ that the present invention is prepared
MnO2@SWCNHs composite material has the principal element of excellent capacitive property.
Claims (9)
1. a kind of Pt/MnO2The preparation method of@carbon nanohorn composite material, which comprises the following steps:
(1) carbon nanohorn is placed in acid solution, in 100~120 DEG C of 8~10h of reflux, is washed out to neutrality, drying is standby
With；
(2) ethylene glycol being added in through step (1) treated carbon nanohorn, then ultrasound is added potassium permanganate, ultrasound 20~
25min, in 100~120 DEG C of 3~5h of reflux；Add K2PtCl620~30min of ultrasound, in 130~150 DEG C of 3~5h of reflux；
The carbon nanohorn, potassium permanganate and K2PtCl6Weight ratio be 1~3:2~5:1.5~3；
(3) washing step (2) products therefrom 5~6 times, are dried overnight in 80~100 DEG C, then in 500~600 DEG C of indifferent gas
Anneal 2~4h in body atmosphere, and Pt/MnO is made2@carbon nanohorn composite material.
2. Pt/MnO according to claim 12The preparation method of@carbon nanohorn composite material, which is characterized in that step
(1) acid solution described in is nitric acid solution.
3. Pt/MnO according to claim 12The preparation method of@carbon nanohorn composite material, which is characterized in that step
(1) detailed process of reflux described in are as follows: in 110 DEG C of reflux 8h.
4. Pt/MnO according to claim 12The preparation method of@carbon nanohorn composite material, which is characterized in that step
(2) carbon nanohorn described in, potassium permanganate and K2PtCl6Weight ratio be 1:5:2.
5. Pt/MnO according to claim 12The preparation method of@carbon nanohorn composite material, which is characterized in that step
(2) after potassium permanganate is added in, in 100 DEG C of oil baths reflux 3h.
6. Pt/MnO according to claim 12The preparation method of@carbon nanohorn composite material, which is characterized in that step
(2) K is added in2PtCl6, in 135 DEG C of oil baths reflux 3h.
7. Pt/MnO according to claim 12The preparation method of@carbon nanohorn composite material, which is characterized in that step
(3) detailed process of washing described in are as follows: respectively respectively three times with distilled water and dehydrated alcohol washing step (2) products therefrom.
8. the Pt/MnO that any one of claim 1~7 the method is prepared2@carbon nanohorn composite material.
9. Pt/MnO according to any one of claims 82@carbon nanohorn composite material is preparing the application in electrode.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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