CN105914051B - One-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite and its preparation method and application - Google Patents
One-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite and its preparation method and application Download PDFInfo
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- CN105914051B CN105914051B CN201610383077.0A CN201610383077A CN105914051B CN 105914051 B CN105914051 B CN 105914051B CN 201610383077 A CN201610383077 A CN 201610383077A CN 105914051 B CN105914051 B CN 105914051B
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002070 nanowire Substances 0.000 claims abstract description 44
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 229910005809 NiMoO4 Inorganic materials 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004202 carbamide Substances 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 11
- 239000003990 capacitor Substances 0.000 abstract description 7
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 11
- 230000004087 circulation Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 230000005611 electricity Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 239000013256 coordination polymer Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite and its preparation method and application, the preparation method include: 1) MnO2The preparation of nano wire monomer;2) by urea, soluble nickel salt, soluble molybdenum hydrochlorate and MnO2Nano wire monomer carries out haptoreaction in water one-dimensional MnO is made2@NiMoO4Nucleocapsid heterojunction composite.The MnO with excellent specific capacitance and cyclical stability can be made by this method2@NiMoO4Composite material is so that the composite material can be competent at the electrode material of electrochemical capacitor, while the preparation method is easy to operate, low in cost, mild condition, environmentally protective.
Description
Technical field
The present invention relates to MnO2@NiMoO4A kind of composite material, and in particular, to one-dimensional MnO2@NiMoO4Nucleocapsid is heterogeneous
Tie composite material and preparation method and application.
Background technique
Supercapacitor, also referred to as electrochemical capacitor, due to its high power density, fast ion exchange rate and long circulating
Service life, therefore it plays an important role in supplement lithium ion battery energy storage cause.
In recent years, in order to find novel, low-cost electrode material, researchers to transition metal material in, by
Have widely in its property with unique physics and chemistry, thus in fields such as catalysis, electrochemistry and gas sensors
Using so as to cause the high interest of people.
The performance of electrochemical capacitor is largely dependent on its electrode material, and current electrode material is mainly transition gold
Belong to material class, such as transition metal oxide and sulfide, mixing transition-metal oxide and conducting polymer etc., it is general single
The defects of that there are specific capacitances is small for one transition metal material, high rate performance is poor, circulation is unstable, so seeking answering for different materials
The synergistic effect of conjunction is critical.Currently, there are many synthesis nanometer transition metal material, Jian Zhu et al. is in Acs Applied
Porous MnO is reported on Materials&Interfaces periodical2Electrode material, but its specific capacitance and cyclical stability are not
It is good.On Nanoscale periodical, Qu Jiangying et al. reports single Mn3O4Only 95F/g.Similarly exist
On Ceramics International periodical, Co that Xing Gao et al. is reported out3O4Electrode material electrochemical properties not yet
It is good, and so on, therefore that there are specific capacitances is small, high rate performance is poor, circulation is unstable for general single transition metal electrode material
The defects of determining.
Summary of the invention
The object of the present invention is to provide a kind of one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite and preparation method thereof and
Using the MnO with excellent specific capacitance and cyclical stability can be made by this method2@NiMoO4Composite material so that
The electrode material that the composite material can be competent at electrochemical capacitor is obtained, while the preparation method is easy to operate, low in cost, item
Part is mild, environmentally protective.
To achieve the goals above, the present invention provides a kind of one-dimensional MnO2@NiMoO4The system of nucleocapsid heterojunction composite
Preparation Method, the preparation method include:
1)MnO2The preparation of nano wire monomer;
2) by urea, soluble nickel salt, soluble molybdenum hydrochlorate and MnO2Nano wire monomer carry out in water haptoreaction with
One-dimensional MnO is made2@NiMoO4Nucleocapsid heterojunction composite.
The present invention also provides a kind of one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite, the one-dimensional MnO2@NiMoO4
Nucleocapsid heterojunction composite is prepared by above-mentioned method.
Invention further provides a kind of above-mentioned one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite is in super electricity
Application in container.
Through the above technical solutions, the present invention passes through urea, soluble nickel salt, soluble molybdenum hydrochlorate and MnO2Nano wire
Monomer carries out haptoreaction by chemical liquid deposition in water, MnO is made2@NiMoO4Composite material, the composite material
Meet one-dimensional nano structure and one-dimensional heterojunction structure simultaneously, so that the composite material has excellent specific capacitance and circulation steady
It is qualitative.
The composite material is due to its excellent chemical property so as to which the electrode material as supercapacitor makes
With specific performance are as follows: under 1A/g current density, the specific capacitance of the composite material can reach 582.2F/g and (sweep speed in 5mV/s
Under, one-dimensional MnO2@NiMoO4The specific capacitance of nucleocapsid heterojunction composite can reach 1123.7F/g);It is recycled by 10000 times
Afterwards, the capacitor of the composite material is still able to maintain more stable, thus also illustrates that the composite material has excellent stability.
In addition, above-mentioned preparation method is easy to operate, low in cost, mild condition and meets environmentally protective requirement, anti-
Should be in the process it is not necessary that any stabilizer, template or surfactant be added, the convenient post-treatment of product is easy to the ruler to material
Very little and pattern is regulated and controled, and large-scale production is suitble to.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the SEM figure under 80,000 times of amplification of A1 in detection example 1;
Fig. 2 is the SEM figure under 9,000 times of amplification of A1 in detection example 1;
Fig. 3 is the TEM figure for detecting A1 in example 1;
Fig. 4 is the EDX figure for detecting A1 in example 1;
Fig. 5 is the XPS figure for detecting A1 in example 1;
Fig. 6 is the XRD diagram for detecting A1 in example 1;
Fig. 7 is the electrochemical impedance spectroscopy test result figure of A1 in application examples 1;
Fig. 8 is cyclic voltammetry (CV) test result figure of A1 in application examples 1;
Fig. 9 is constant current charge-discharge (CP) test result figure of A1 in application examples 1;
Figure 10 is the cycle performance testing result figure of A1 in application examples 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of one-dimensional MnO2@NiMoO4The preparation method of nucleocapsid heterojunction composite, the preparation method
Include:
1)MnO2The preparation of nano wire monomer;
2) by urea, soluble nickel salt, soluble molybdenum hydrochlorate and MnO2Nano wire monomer carry out in water haptoreaction with
One-dimensional MnO is made2@NiMoO4Nucleocapsid heterojunction composite.
In the step 2) of above-mentioned preparation method, the dosage of each material can select in a wide range, but in order to make
Obtaining composite material obtained has superior specific capacitance and cyclical stability, it is preferable that the MnO relative to 0.2-0.6mmol2
Nano wire monomer, the dosage of urea are 2-6mmol, and the dosage of soluble nickel salt is 1-3mmol, and the dosage of soluble molybdenum hydrochlorate is
1-3mmol;
In the step 2) of above-mentioned preparation method, the dosage of water can select in a wide range, but in order to enable system
The composite material obtained has superior specific capacitance and cyclical stability, it is preferable that the MnO of 0.2-0.6mmol2Nano wire list
Body, the dosage of water are 10-40mL.
In the step 2) of above-mentioned preparation method, catalytic actual conditions can select in a wide range, still
In order to enable composite material obtained has superior specific capacitance and cyclical stability, it is preferable that haptoreaction at least meets
The following conditions: Contact Temperature is 100-140 DEG C, time of contact 8-16h;
In the step 2) of above-mentioned preparation method, the specific type of soluble nickel salt and soluble molybdenum hydrochlorate can be wide
Selection in range, but in order to enable composite material obtained has superior specific capacitance and cyclical stability, it is preferable that it can
Insoluble nickel salt is selected from one of nickel chloride, nickel nitrate and nickel sulfide or a variety of, and soluble molybdenum hydrochlorate is selected from sodium molybdate ammonium molybdate
One of or it is a variety of.
In the step 2) of above-mentioned preparation method, the filling sequence of raw material can select in a wide range, can be one
Step mixing can also carry out substep mixing, but in order to enable composite material obtained has superior specific capacitance and circulation
Stability, it is preferable that in step 2), the filling sequence of raw material are as follows: first by MnO2Nano wire monomer is dispersed in water to form MnO2
Then urea and soluble nickel salt are added to MnO for nano wire monomer solution2It is stirred in nano wire monomer solution,
Then soluble molybdenum hydrochlorate is added and carries out ultrasonic vibration to carry out haptoreaction;
In above-mentioned gradually mixed process, the actual conditions of stirring and ultrasonic vibration can change in a wide range, but
Be in order to enable being sufficiently mixed between each material, it is preferable that stirring at least meets the following conditions: whipping temp is 15-35 DEG C, is stirred
Mixing the time is 10-60min;Ultrasonic vibration at least meets the following conditions: ultrasonic temperature is 15-35 DEG C, ultrasonic time 3-
10min。
In the present invention, MnO2Nano wire monomer can use commercially available product, can also be by now-making-now-using, in order to prevent
MnO2Nano wire monomer is rotten, it is preferable that in step 1), MnO2The specific steps of the preparation of nano wire monomer are as follows: will be soluble
Permanganate, soluble ammonium salt and water carry out hydro-thermal reaction so that MnO is made2Nano wire monomer.
In above-mentioned hydro-thermal reaction, the dosage of each material can select in a wide range, but produce MnO to improve2
The yield of nano wire monomer, it is preferable that relative to the soluble permanganate of 0.4mmol, the dosage of soluble ammonium salt is 0.3-
0.5mmol, the dosage of water are 10-30mL.
In above-mentioned hydro-thermal reaction, the actual conditions of hydro-thermal reaction can select in a wide range, but in order to improve
Produce MnO2The yield of nano wire monomer, it is preferable that hydro-thermal reaction at least meets the following conditions: reaction temperature is 170-190 DEG C, instead
It is 18-22h between seasonable.
The present invention also provides a kind of one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite, the one-dimensional MnO2@NiMoO4
Nucleocapsid heterojunction composite is prepared by above-mentioned method.
Invention further provides a kind of above-mentioned one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite is in super electricity
Application in container.
The present invention will be described in detail by way of examples below.
Preparation example
MnO2The preparation of nano wire monomer:
By the KMnO of 10ml4The NH of aqueous solution (0.04mol/L) and 10ml4Cl aqueous solution (0.04mol/L) is at 180 DEG C
It reacts 20h and MnO is made2Nano wire monomer.
Embodiment 1
1) by MnO2MnO is made in nano wire monomer (0.4mmol) ultrasonic disperse 3min in 20mL water2Nano wire monomer water
Solution;
2) above-mentioned MnO is added in 4mmol urea, 1mmol nickel chloride2It is stirred in nano wire monomer solution and at 25 DEG C
30min;It is subsequently added into 1mmol sodium molybdate and the ultrasonic vibration 5min at 25 DEG C;It is subsequently placed at 110 DEG C and reacts 12h;It is last cold
But, respectively washed with deionized water and dehydrated alcohol and dried at 3 times, 60 DEG C one-dimensional MnO is made respectively2@NiMoO4Nucleocapsid is heterogeneous
Tie composite A 1.
Embodiment 2
1) by MnO2MnO is made in nano wire monomer (0.5mmol) ultrasonic disperse 5min in 20mL water2Nano wire monomer water
Solution;
2) above-mentioned MnO is added in 5mmol urea, 2mmol nickel chloride2It is stirred in nano wire monomer solution and at 25 DEG C
30min;It is subsequently added into 2mmol sodium molybdate and the ultrasonic vibration 5min at 25 DEG C;It is subsequently placed at 120 DEG C and reacts 10h;It is last cold
But, respectively washed with deionized water and dehydrated alcohol and dried at 3 times, 60 DEG C one-dimensional MnO is made respectively2@NiMoO4Nucleocapsid is heterogeneous
Tie composite A 2.
Embodiment 3
1) by MnO2MnO is made in nano wire monomer (0.3mmol) ultrasonic disperse 6min in 15mL water2Nano wire monomer water
Solution;
2) above-mentioned MnO is added in 3mmol urea, 1.5mmol nickel chloride2It is stirred in nano wire monomer solution and at 25 DEG C
Mix 30min;It is subsequently added into 1.5mmol sodium molybdate and the ultrasonic vibration 5min at 25 DEG C;It is subsequently placed at 130 DEG C and reacts 8h;Most
It cools down afterwards, respectively washed with deionized water and dehydrated alcohol dry at 3 times, 60 DEG C one-dimensional MnO is made respectively2@NiMoO4Nucleocapsid
Heterojunction composite A3.
Embodiment 4
1) by MnO2MnO is made in nano wire monomer (0.6mmol) ultrasonic disperse 8min in 30mL water2Nano wire monomer water
Solution;
2) above-mentioned MnO is added in 6mmol urea, 3mmol nickel chloride2It is stirred in nano wire monomer solution and at 25 DEG C
30min;It is subsequently added into 3mmol sodium molybdate and the ultrasonic vibration 5min at 25 DEG C;It is subsequently placed at 140 DEG C and reacts 8h;It is last cold
But, respectively washed with deionized water and dehydrated alcohol and dried at 3 times, 60 DEG C one-dimensional MnO is made respectively2@NiMoO4Nucleocapsid is different
Matter knot composite A 4.
Embodiment 5
1) by MnO2MnO is made in nano wire monomer (0.2mmol) ultrasonic disperse 3min in 10mL water2Nano wire monomer water
Solution;
2) above-mentioned MnO is added in 2mmol urea, 1mmol nickel chloride2It is stirred in nano wire monomer solution and at 25 DEG C
30min;It is subsequently added into 1mmol sodium molybdate and the ultrasonic vibration 5min at 25 DEG C;It is subsequently placed at 100 DEG C and reacts 16h;It is last cold
But, respectively washed with deionized water and dehydrated alcohol and dried at 3 times, 60 DEG C one-dimensional MnO is made respectively2@NiMoO4Nucleocapsid is heterogeneous
Tie composite A 5.
Detect example 1
1) morphology analysis is carried out to A1 with scanning electron microscope (SEM), as a result as shown in Fig. 1 and Fig. 2, the chart is bright
A1 is one-dimensional nano structure.
2) A1 is analyzed with transmission electron microscope (TEM), as a result as shown in figure 3, the bright A1 of the chart is one-dimensional
Heterojunction structure.
3) A1 is analyzed with X-ray energy spectrum (EDX), as a result as shown in figure 4, the figure shown A1 contain Mn, Ni,
Mo, O element.
4) element valence of A1 is analyzed with x-ray photoelectron spectroscopy (XPS), as a result such as Fig. 5, the change of Mn element
Conjunction valence is+4, and corresponding compound should be MnO2;The chemical valence of Ni element is that the chemical valence of+2, Mo element is+6, correspondingization
Closing object should be NiMoO4, so A1 is MnO2@NiMoO4Composite material.
5) A1 is detected with X-ray diffraction (XRD), as a result as shown in fig. 6, obtaining map and JCPDS standard card
MnO corresponding to NO.72-19822NiMoO corresponding to diffraction maximum and JCPDS standard card NO.45-01424Diffraction maximum
It fits like a glove, further explanation A1 is MnO2@NiMoO4Composite material.
Similarly, A2-A5 is detected, the testing result of testing result and A1 are almost the same, to also illustrate A2-
A5 is MnO2@NiMoO4One-dimensional nano heterogeneous knot composite material.
Application examples 1
The memory on Shanghai Chen Hua Instrument Ltd. manufacture CHI660E electrochemical workstation is tested below.It surveys below
Examination is all made of three-electrode system, wherein by MnO2@NiMoO4Composite A 1, acetylene black, polytetrafluoroethylene (PTFE) (PTFE) are according to 6:
The weight ratio mixing of 2:2 is used as working electrode (A1 electrode), using platinum electrode as to electrode, with saturated calomel electrode (SCE)
As reference electrode;Using the KOH solution of 2M as electrolyte.
(1) electrochemical impedance spectroscopy is tested:
A1 electrode ac impedance spectroscopy comparing result before and after the circle of circulation 5000 is obtained by electrochemical impedance spectroscopy, is such as schemed
Shown in 7, circle point curve indicates that the AC impedance curve of A1 electrode before the loop, square curve indicate that A1 electrode is followed in 5000 circles
AC impedance curve after ring.
Ac impedance spectroscopy is divided into high frequency region part and low frequency range part, by the arc and low frequency range of one section of semicircle of high frequency region
A skew lines composition.In the internal resistance that the intersection point of high frequency region impedance spectrum and real axis is A1 electrode, including active material itself
The contact resistance of resistance, the resistance of electrolyte and active material and electrolyte.In high frequency region it can be found that A1 electrode is in circulation
Curve approximation when after preceding and 5000 circulations, the curve of high frequency region is before the loop with circulation later closer to excellent
Supercapacitor electrode material, being indicated above A1 electrode can be used as the electrode material of supercapacitor.
(2) cyclic voltammetry (CV) is tested
Respectively with 5mV s-1、10mV s-1、15mV s-1、20mV s-1、25mV s-1With 30mV s-1Sweep speed carry out
Scanning obtains the cyclic voltammetry curve of A1 as shown in figure 8, the potential range of the curve is 0-0.5V.Gone out by CV graphic calculation than electricity
Hold, i.e. A1 is in 5mV s-1Sweeping specific capacitance under speed is 1123.7F g-1, illustrate that A1 has the performance of excellent storage electricity.Its
In, capacitor calculation formula are as follows:I is size of current, and v is to sweep speed, and △ V is potential difference, and m is
The quality of working electrode on piece sample.
(3) constant current charge-discharge (CP) is tested
Respectively in 1A g-1、2A g-1、4A g-1、6A g-1、8A g-1With 10A g-1Lower progress constant current charge-discharge detection, obtains
Constant current charge-discharge curve of the A1 under different current densities out, as shown in Figure 9.Wherein, ordinate, that is, voltage range of the curve
For 0-0.45V.The specific capacitance charge and discharge under different current densities are calculated by following equation.Gone out by charge and discharge graphic calculation than electricity
Hold, i.e. A1 is in 1A g-1Specific capacitance is 582.2F g under current density-1, illustrate that A1 has the performance of excellent storage electricity.Its
In, capacitor calculation formula are as follows: Cm=(It)/(△ Vm), I are size of current, and t is discharge time, and △ V is potential difference, m
For the quality of working electrode on piece sample.
(4) cycle performance detects
In 40mV s-1It sweeps and is recycled 5000 times under speed, obtain circulation-specific capacitance curve of A1, the results are shown in Figure 10, will most
Whole capacity and initial capacity comparison it is found that by 5000 times circulation after it is close with initial capacitance, illustrate A1 have excellent stabilization
Property.
Similarly, A2-A5 progress electrochemical impedance spectroscopy test detection, cyclic voltammetry (CV) test, constant current are filled
The testing result of electric discharge (CP) test and cycle performance detection, testing result and A1 are almost the same, to also illustrate that A2-A5 has
There are excellent specific capacitance and cyclical stability.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (6)
1. a kind of one-dimensional MnO2@NiMoO4The preparation method of nucleocapsid heterojunction composite, which is characterized in that the preparation method
Include:
1)MnO2The preparation of nano wire monomer;
2) by urea, soluble nickel salt, soluble molybdenum hydrochlorate and the MnO2Nano wire monomer carries out haptoreaction in water to make
Obtain one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite;
The MnO relative to 0.2-0.6mmol2Nano wire monomer, the dosage of the urea are 2-6mmol, the soluble nickel
The dosage of salt is 1-3mmol, and the dosage of the soluble molybdenum hydrochlorate is 1-3mmol;The MnO relative to 0.2-0.6mmol2
Nano wire monomer, the dosage of the water are 10-40mL;The haptoreaction at least meets the following conditions: Contact Temperature 100-
140 DEG C, time of contact 8-16h;The soluble nickel salt is selected from one of nickel chloride, nickel nitrate and nickel sulfate or a variety of,
The soluble molybdenum hydrochlorate is selected from one of sodium molybdate, ammonium molybdate or a variety of;
In step 2), the filling sequence of raw material are as follows: first by MnO2Nano wire monomer is dispersed in water to form MnO2Nano wire monomer
Then urea and soluble nickel salt are added to the MnO for aqueous solution2Be stirred in nano wire monomer solution, then plus
Enter soluble molybdenum hydrochlorate and carries out ultrasonic vibration to carry out haptoreaction;The stirring at least meets the following conditions: whipping temp
It is 15-35 DEG C, mixing time 10-60min;The ultrasonic vibration at least meets the following conditions: ultrasonic temperature is 15-35 DEG C,
Ultrasonic time is 3-10min.
2. preparation method according to claim 1, wherein in step 1), the MnO2The tool of the preparation of nano wire monomer
Body step are as follows: soluble permanganate, soluble ammonium salt and water are subjected to hydro-thermal reaction so that the MnO is made2Nano wire monomer.
3. preparation method according to claim 2, wherein described solvable relative to the soluble permanganate of 0.4mmol
Property ammonium salt dosage be 0.3-0.5mmol, the dosage of the water is 10-30mL.
4. preparation method according to claim 3, wherein the hydro-thermal reaction at least meets the following conditions: reaction temperature
It is 170-190 DEG C, reaction time 18-22h.
5. a kind of one-dimensional MnO2@NiMoO4Nucleocapsid heterojunction composite, which is characterized in that the one-dimensional MnO2@NiMoO4Nucleocapsid
Heterojunction composite is prepared by method described in any one of claim 1-4.
6. a kind of one-dimensional MnO according to claim 52@NiMoO4Nucleocapsid heterojunction composite is in supercapacitor
Using.
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CN106449176A (en) * | 2016-11-22 | 2017-02-22 | 安徽师范大学 | One-dimensional manganese dioxide@nickel cobaltate core-shell heterostructure composite as well as preparation method and application thereof |
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CN107017092A (en) * | 2017-04-26 | 2017-08-04 | 安徽师范大学 | A kind of one-dimensional MnO2@NiO nucleocapsid heterojunction composites and its preparation method and application |
CN109148160A (en) * | 2018-08-06 | 2019-01-04 | 安徽师范大学 | A kind of core-shell structure manganese cobalt/cobalt oxide@nickel cobalt oxide composite material and preparation method and application |
CN109461591B (en) * | 2018-10-29 | 2020-05-05 | 安徽师范大学 | Manganese dioxide nanotube @ Ni-Co LDH/cobalt disulfide nanocage composite material and preparation method and application thereof |
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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 |
CN110180569A (en) * | 2019-05-23 | 2019-08-30 | 武汉科技大学 | Sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method |
CN113101946B (en) * | 2021-03-10 | 2022-03-25 | 华南理工大学 | NiMoO4Base Z-type heterojunction photocatalyst and preparation and application thereof |
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