CN103413691B - A kind of MnO for ultracapacitor2the preparation method of/carbon composite - Google Patents
A kind of MnO for ultracapacitor2the preparation method of/carbon composite Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 33
- 238000001354 calcination Methods 0.000 claims abstract description 29
- 238000001291 vacuum drying Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000005119 centrifugation Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- 229930091371 Fructose Natural products 0.000 claims abstract description 5
- 239000005715 Fructose Substances 0.000 claims abstract description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 5
- 229930006000 Sucrose Natural products 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000005720 sucrose Substances 0.000 claims abstract description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims 2
- 239000003990 capacitor Substances 0.000 abstract description 12
- 238000012546 transfer Methods 0.000 abstract description 10
- 239000007772 electrode material Substances 0.000 abstract description 7
- 239000012286 potassium permanganate Substances 0.000 abstract description 3
- 239000008187 granular material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process 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
- 238000001453 impedance spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A kind of MnO for ultracapacitor2The preparation method of/carbon composite, is dissolved in glucose or sucrose or fructose in deionized water, after stirring to clarify solution, is transferred in hydrothermal reaction kettle；Gained precursor solution by centrifugation, washing, alcohol wash, be dried, prepare single dispersing carbon ball；Step 2, take single dispersing carbon ball heat treated in concentrated NaOH solution, then, after centrifugal for mixture solution, washing, alcohol being washed each 3 times, it is dried, calcination processing in vacuum or inert atmosphere, step 3, with the carbon ball after step 2 modification as template, be placed in KMnO4In aqueous solution, ageing is stirred at room temperature, is precipitated, by pelleting centrifugation, after washing, alcohol are washed, be dried in vacuum drying oven, obtain CS@MnO2Parcel powder；Prepared MnO2/ carbon ball composite granule presents nucleocapsid structure, and specific surface area is up to 778m2/ more than g, specific capacity reaches more than 439F/g, and charge transfer resistance is less than 2.1 Ω, is a kind of novel electrode material for super capacitor.
Description
Technical field
The present invention relates to technical field of new energy material preparation, particularly to a kind of MnO for ultracapacitor2/ carbon
The preparation method of composite.
Background technology
Ultracapacitor as a kind of Novel energy storage apparatus, have have extended cycle life, charge/discharge rates is fast, power is high and
The feature such as environmentally friendly, therefore suffers from the extensive concern of domestic and international scientist.The kind of ultracapacitor presses its operation principle
Double layer capacitor, Faraday pseudo-capacitance device can be divided into.Double layer capacitor, based on double electrode layer theory, utilizes electrode and electrolysis
The interfacial electric double layer electric capacity formed between matter stores energy.Faradic pseudo-capacitor is then based on Faradaic processes, i.e. at farad
Produce during the electrochemical change of electric charge transfer, not only occur on electrode surface, and electrode interior can be goed deep into, therefore
Capacitance more higher than double layer capacitor and energy density can be obtained.
For developing the ultracapacitor of function admirable, having relatively of the most applicable vital supercapacitor applications
The exploitation of the electrode material of height ratio capacity, selected electrode material must easily be formed higher double in electrode/electrolyte interface
Electric layer electric capacity or Faraday pseudo-capacitance, and there is suitable mechanical stability, and good ion, electron conduction.At present
It is concentrated mainly on carbon-based material and the research of transition metal oxide material.Wherein carbon-based material mainly utilizes bigger serface to produce
Raw electric double layer capacitance amount, and macropore and the mesoporous potential polarization advantageously reduced under high current density, micropore then helps
In increasing specific surface area, increase and compare electric capacity.In nearest research, the research to noble metal oxide electrodes capacitor, mainly
Use RuO2, IrO2Deng metal oxide containing precious metals as electrode material, due to RuO2The electric conductivity of electrode is better than carbon electrode, and electrode exists
Sulphuric acid is stablized, it is possible to obtain higher specific energy, is the electrode material of a kind of excellent performance, and the capacitor of preparation compares carbon electrode
Capacitor has better performance, therefore has good development prospect.But, owing to resource-constrained, the price of noble metal are held high
The expensive use limiting it.The oxide of transition metal system, due to the multiple oxidation states of metallic atom, the most alive effect
Under, quick redox reaction can be produced greatly, from this ultimate principle, it is contemplated that be positioned at the periodic table of elements
The oxide of transition metal region element all can have the fake capacitance performance similar to ruthenium-oxide.Proving after deliberation, manganese oxide is equal
Having preferable supercapacitor properties, developing these succedaneum is an important developing direction.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, it is an object of the invention to provide a kind of for ultracapacitor
MnO2The preparation method of/carbon composite, with the dispersed nano carbon ball (Carbon sphere is called for short CS) of water heat transfer
For template, pass through KMnO4Solution forms MnO with the redox reaction on carbon ball surface at carbon ball surface in situ2Layer, passes through hydro-thermal
Condition controls the size of carbon ball masterplate, is controlled the activity of its surface reduction group by carbon ball heat treatment condition, by used
KMnO4Concentration, reaction temperature and response time condition control the degree that redox reaction is carried out, and then reach to control MnO2Layer
With the proportional amount of purpose of the carbon ball heart, finally prepare MnO2/ carbon ball composite structural ceramic powder body；This powder product is simultaneously
Possess electric double layer capacitance and the MnO of porous carbon2Fake capacitance；By the regulation to each synthesis condition in experimentation, obtaining
While must having high-specific surface area, hierarchical porous structure, material is also made to have high specific capacity and low charge transfer resistance, with
Meet its application requirement on ultracapacitor.
In order to achieve the above object, the technical scheme is that
A kind of MnO for ultracapacitor2The preparation method of/carbon composite, comprises the following steps:
Step one, 60-120g glucose or sucrose or fructose are dissolved in 900mL deionized water, stir to clarify solution
After, it is transferred in 1000mL hydrothermal reaction kettle；150-250 DEG C, 900r/min rotating speed, hydro-thermal 1-10h, gained precursor solution warp
After centrifugal, washing, alcohol wash each 3 times, 50-80 DEG C of vacuum drying oven is dried 10-20h, prepares single dispersing carbon ball；
Step 2, take 1-5g single dispersing carbon ball heat treated in 100-1000mL, 0.5M-5M concentrated NaOH solution, heating
Temperature is 50-90 DEG C, and heat time heating time is 0.5-12h, after then centrifugal for mixture solution, washing, alcohol being washed each 3 times, at 50-80
Being dried 10-20h in DEG C vacuum drying oven, gained solid calcination processing in vacuum or inert atmosphere again, calcining heat is 300-
1000 DEG C, calcination time is 0.5-5h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 100-1000mL, 2.5-25g/L4
In aqueous solution, ageing 0.5-5h is stirred at room temperature, is precipitated, by pelleting centrifugation, after washing, alcohol wash each 3 times, true in 50-80 DEG C
Empty baking oven is dried 10～20h, obtains CS@MnO2Parcel powder.
The MnO that specific surface area is big, higher than electric capacity, power density is high can be obtained by above-mentioned technique2/ carbon ball composite ceramics
Powder body.
The method comprises the steps of firstly, preparing surface and there is the carbon ball of reproducibility oxygen-containing functional group, then by later stage modification,
Improve carbon ball electric conductivity, reduce its surface reduction simultaneously.Recycle KMnO on this basis4Strong oxidizing property and carbon ball surface
Reproducibility radical reaction, carbon ball deposits certain thickness MnO2Layer, obtains MnO2/ carbon ball composite construction.This special
Complex nucleus shell structure, when as ultracapacitor, is provided simultaneously with electric double layer storage and the MnO of porous carbon2Faraday pseudo-capacitance
Mechanism, therefore has the highest specific capacity.It addition, its electrically conductive core can be substantially reduced charge transfer resistance, product is made to have
Higher power density.Preparation technology of the present invention is simple, and the requirement to material system is low, is thus advantageous to popularization and application.
The present invention in two kinds of mechanism of storage electric charge, designs a kind of nucleocapsid structure according to ultracapacitor dexterously
MnO2/ carbon ball composite, it both can utilize the electric double layer of heart portion porous carbon former when as electrode material for super capacitor
Reason storage electric charge, it is also possible to the MnO outside Li Yonging2Faraday's principle storage electric charge that layer provides, thus obtain the highest specific volume
Amount.It addition, be the power density improving ultracapacitor further, the present invention is at MnO2Integument is formed front to single dispersing carbon ball
It is modified processing, to improve the electric conductivity of powder body, solves MnO2The material problem that resistance is excessive when as super capacitor.Institute
The MnO of preparation2/ carbon ball composite granule presents nucleocapsid structure, and specific surface area is up to 778m2/ more than g, specific capacity reach 439F/g with
On, charge transfer resistance is less than 2.1 Ω, is a kind of novel electrode material for super capacitor.
Accompanying drawing explanation
Fig. 1 is the microstructure schematic diagram of single dispersing carbon ball template, and wherein Fig. 1 (a) is SEM photograph；Fig. 1 (b) is that TEM shines
Sheet.
Fig. 2 is MnO2The microstructure schematic diagram of/carbon ball composite structural ceramic powder body, wherein Fig. 2 (a) is SEM photograph, figure
2(b) TEM photo, Fig. 2 (c) BJH curve.
Fig. 3 (a) is product TEM partial enlarged drawing, and Fig. 3 (b) is product TEM high-resolution photo, and Fig. 3 (c) is product model,
Fig. 3 (d) is the cyclic voltammetry curve under different voltage scan rate, and Fig. 3 (e) is constant current charge-discharge curve, and Fig. 3 (f) is impedance
Spectrum.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in detail.
Embodiment one
The present embodiment comprises the following steps:
Step one, 60g sucrose is dissolved in 900mL deionized water, after stirring to clarify solution, is transferred to 1000mL hydro-thermal
In reactor, 150 DEG C, 900r/min rotating speed, hydro-thermal 6h, gained precursor solution by centrifugation, washing, after alcohol washes each 3 times, 60
DEG C vacuum drying oven is dried 12h, prepares single dispersing carbon ball；
Step 2, taking 1g single dispersing carbon ball heat treated in the NaOH solution of the 0.5M of 500mL, heating-up temperature is 50
DEG C, heat time heating time is 12h, after then centrifugal for mixture solution, washing, alcohol being washed each 3 times, is dried in 50 DEG C of vacuum drying ovens
12h, gained solid calcination processing in argon gas atmosphere stove again, calcining heat is 1000 DEG C, and calcination time is 0.5h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 200mL, 5g/L4In aqueous solution,
Ageing 5h is stirred at room temperature, is precipitated, by pelleting centrifugation, after washing, alcohol wash each 3 times, in 60 DEG C of vacuum drying ovens, be dried 12h,
Obtain CS@MnO2Parcel powder.
From Fig. 1 it is observed that prepared C ball template dispersibility is preferable, average diameter is 300nm.Wrap up from Fig. 2
MnO2After the SEM photograph of carbon ball and TEM photo it can be seen that C ball surface becomes coarse, surface attachment a lot of nanometer wire
MnO2, integument thickness is about 20nm.N2Adsorption-desorption curve explanation gained powder body about 3.4nm's is mesoporous, and this mainly comes
From in the porous carbon of core, the specific surface area calculating powder body is 1032m2/g.Fig. 3 reflects MnO2/ carbon ball composite structural ceramic
The micro-structural feature of powder body and capacitive property, from Fig. 3 (a), the TEM photo of partial enlargement can be seen that MnO2Integument exists
Presenting bar-shaped on porous carbon ball, Fig. 3 (b) reflects the MnO of outer layer2Crystallinity is fine, this structure not only improve ionic adsorption,
Desorption, is simultaneously also beneficial to the embedding of ion and extracts, thus improving fake capacitance performance.Micro-knot according to Fig. 3 (a) He (b)
Structure feature, we establish product functional mode when as ultracapacitor, as shown in Fig. 3 (c) figure.Circulation in Fig. 3 (d)
Volt-ampere curve presents the rectangle of symmetry, is typical capacitive properties, and when increasing to 75mv/s along with sweep speed, cyclic voltammetric is bent
Line rectangular shape is deteriorated.This is because when low sweep speed, the electronics in solution can be with carbon ball and MnO2Layer is fully contacted, and sends out
Raw reversible reaction；But when too high sweep speed, the electronics of electrode surface has little time reaction, be equivalent to resistance and increase, cause electricity
Pole charge-discharge performance declines, so its cyclic voltammetry curve shape changes.By the constant current charge-discharge curve in Fig. 3 (e)
We are it appeared that in the range of 0～0.9V, charging curve and discharge curve have comparatively ideal symmetry, and MnO is described2/ carbon ball
Composite structural ceramic powder body oxidation reaction conducted in the electrolyte solution and reduction reaction are reversible, by calculating
MnO2The specific capacity of/carbon ball composite structural ceramic powder body reaches 583F/g.Known by the data of Fig. 3 (f) middle impedance spectrum high frequency region, electricity
In the solution of pole, charge transfer resistance is 1.2 Ω, illustrates that heart portion carbon ball has extraordinary electric conductivity.Therefore this material can conduct
A kind of super capacitor material of novel high-performance.
Embodiment two
The present embodiment comprises the following steps:
Step one, 80g fructose is dissolved in 900mL deionized water, after stirring to clarify solution, is transferred to 1000mL hydro-thermal
In reactor, 170 DEG C, 900r/min rotating speed, hydro-thermal 3h, gained precursor solution by centrifugation, washing, after alcohol washes each 3 times, 60
DEG C vacuum drying oven is dried 12h, prepares single dispersing carbon ball；
Step 2, taking 1.5g single dispersing carbon ball heat treated in the 2M NaOH solution of 200mL, heating-up temperature is 70 DEG C,
Heat time heating time is 8h, after then centrifugal for mixture solution, washing, alcohol being washed each 3 times, is dried 15h, institute in 60 DEG C of vacuum drying ovens
Solid again in vacuum drying oven calcination processing, calcining heat is 700 DEG C, and calcination time is 2h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 500mL, 10g/L4In aqueous solution,
Ageing 4h is stirred at room temperature, is precipitated, by pelleting centrifugation, after washing, alcohol wash each 3 times, in 60 DEG C of vacuum drying ovens, be dried 12h,
Obtain CS@MnO2Parcel powder.
Measurement powder specific-surface area detection is 974m2/ g, specific capacity is 557F/g, and charge transfer resistance is 1.0 Ω.
Embodiment three
The present embodiment comprises the following steps:
Step one, 100g glucose are dissolved in 900mL deionized water, after stirring to clarify solution, are transferred to 1000mL water
In thermal response still, 200 DEG C, 900r/min rotating speed, hydro-thermal 3h；Gained precursor solution by centrifugation, washing, after alcohol washes each 3 times,
60 DEG C of vacuum drying ovens are dried 12h, prepare C ball.
Step 2, take 3g dried C ball, 80 DEG C of heated and stirred 6h in 750mL, 5M NaOH solution, then will mixing
After thing solution centrifugal, washing, alcohol wash each 3 times, 80 DEG C of vacuum drying ovens are dried 12h.Gained solid is forged in argon gas atmosphere again
Burning processes, and calcining heat is 800 DEG C, and calcination time is 2h.
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 800mL, 15g/L4In aqueous solution,
Ageing 1h is stirred at room temperature, is precipitated, by pelleting centrifugation, after washing, alcohol wash each 3 times, in 60 DEG C of vacuum drying ovens, be dried 12h,
Obtain CS@MnO2Parcel powder.
Measurement powder specific-surface area detection is 902m2/ g, specific capacity is 495F/g, and charge transfer resistance is 1.4 Ω.
Embodiment four
The present embodiment comprises the following steps:
Step one, 120g glucose are dissolved in 900mL deionized water, after stirring to clarify solution, are transferred to 1000mL water
In thermal response still, 220 DEG C, 900r/min rotating speed, hydro-thermal 4h；Gained precursor solution by centrifugation, washing, after alcohol washes each 3 times,
60 DEG C of vacuum drying ovens are dried 12h, prepare C ball；
Step 2, take 5g dried C ball, 90 DEG C of heated and stirred 4h in 1000mL, 3M NaOH solution, then will be mixed
After polymer solution is centrifugal, washing, alcohol washes each 3 times, 80 DEG C of vacuum drying ovens are dried 12h.Gained solid is again in argon gas atmosphere
Calcination processing, calcining heat is 900 DEG C, and calcination time is 1h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 1000mL, 2.5g/L4Aqueous solution
In, ageing 5h is stirred at room temperature, is precipitated, by pelleting centrifugation, after washing, alcohol wash each 3 times, be dried in 60 DEG C of vacuum drying ovens
12h, obtains CS@MnO2Parcel powder.
Measurement powder specific-surface area detection is 778m2/ g, specific capacity is 439F/g, and charge transfer resistance is 2.1 Ω.
Claims (5)
1. the MnO for ultracapacitor2The preparation method of/carbon composite, comprises the following steps:
Step one, 60-120g glucose or sucrose or fructose are dissolved in 900mL deionized water, after stirring to clarify solution, turn
Move in 1000mL hydrothermal reaction kettle；150-250 DEG C, 900r/min rotating speed, hydro-thermal 1-10h, gained precursor solution by centrifugation,
After washing, alcohol wash each 3 times, 50-80 DEG C of vacuum drying oven is dried 10-20h, prepares single dispersing carbon ball；
Step 2, take 1-5g single dispersing carbon ball heat treated, heating-up temperature in 100-1000mL, 0.5M-5M concentrated NaOH solution
For 50-90 DEG C, heat time heating time is 0.5-12h, after then centrifugal for mixture solution, washing, alcohol being washed each 3 times, true at 50-80 DEG C
Being dried 10-20h in empty baking oven, gained solid calcination processing in vacuum or inert atmosphere again, calcining heat is 300-1000
DEG C, calcination time is 0.5-5h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 100-1000mL, 2.5-25g/L4Water-soluble
In liquid, ageing 0.5-5h is stirred at room temperature, is precipitated, by pelleting centrifugation, after washing, alcohol wash each 3 times, dry in 50-80 DEG C of vacuum
Case is dried 10～20h, obtains CS@MnO2Parcel powder.
A kind of MnO for ultracapacitor the most according to claim 12The preparation method of/carbon composite, including with
Lower step:
Step one, 60g sucrose is dissolved in 900mL deionized water, after stirring to clarify solution, is transferred to 1000mL hydro-thermal reaction
In still, 150 DEG C, 900r/min rotating speed, hydro-thermal 6h, gained precursor solution by centrifugation, washing, after alcohol washes each 3 times, true at 60 DEG C
Empty baking oven is dried 12h, prepares single dispersing carbon ball；
Step 2, taking 1g single dispersing carbon ball heat treated in the NaOH solution of the 0.5M of 500mL, heating-up temperature is 50 DEG C, adds
The heat time is 12h, after then centrifugal for mixture solution, washing, alcohol being washed each 3 times, is dried 12h, institute in 50 DEG C of vacuum drying ovens
Obtaining solid calcination processing in argon gas atmosphere stove again, calcining heat is 1000 DEG C, and calcination time is 0.5h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 200mL, 5g/L4In aqueous solution, room temperature is stirred
Mix ageing 5h, be precipitated, by pelleting centrifugation, after washing, alcohol wash each 3 times, in 60 DEG C of vacuum drying ovens, be dried 12h, obtain CS@
MnO2Parcel powder.
A kind of MnO for ultracapacitor the most according to claim 12The preparation method of/carbon composite, including with
Lower step:
Step one, 80g fructose is dissolved in 900mL deionized water, after stirring to clarify solution, is transferred to 1000mL hydro-thermal reaction
In still, 170 DEG C, 900r/min rotating speed, hydro-thermal 3h, gained precursor solution by centrifugation, washing, after alcohol washes each 3 times, true at 60 DEG C
Empty baking oven is dried 12h, prepares single dispersing carbon ball；
Step 2, taking 1.5g single dispersing carbon ball heat treated in the 2M NaOH solution of 200mL, heating-up temperature is 70 DEG C, heating
Time is 8h, after then centrifugal for mixture solution, washing, alcohol being washed each 3 times, is dried 15h in 60 DEG C of vacuum drying ovens, and gained is solid
Body is again in vacuum drying oven calcination processing, and calcining heat is 700 DEG C, and calcination time is 2h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 500mL, 10g/L4In aqueous solution, room temperature
Stirring ageing 4h, is precipitated, and by pelleting centrifugation, after washing, alcohol wash each 3 times, is dried 12h, obtains in 60 DEG C of vacuum drying ovens
CS@MnO2Parcel powder.
A kind of MnO for ultracapacitor the most according to claim 12The preparation method of/carbon composite, including with
Lower step:
Step one, 100g glucose are dissolved in 900mL deionized water, after stirring to clarify solution, are transferred to 1000mL hydro-thermal anti-
Answer in still, 200 DEG C, 900r/min rotating speed, hydro-thermal 3h, gained precursor solution by centrifugation, washing, after alcohol washes each 3 times, at 60 DEG C
Vacuum drying oven is dried 12h, prepares C ball；
Step 2, take 3g dried C ball, 80 DEG C of heated and stirred 6h in 750mL, 5M NaOH solution, then that mixture is molten
After liquid is centrifugal, washing, alcohol washes each 3 times, 80 DEG C of vacuum drying ovens are dried 12h；Gained solid is again in argon gas atmosphere at calcining
Reason, calcining heat is 800 DEG C, and calcination time is 2h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 800mL, 15g/L4In aqueous solution, room temperature
Stirring ageing 1h, is precipitated, and by pelleting centrifugation, after washing, alcohol wash each 3 times, is dried 12h, obtains in 60 DEG C of vacuum drying ovens
CS@MnO2Parcel powder.
A kind of MnO for ultracapacitor the most according to claim 12The preparation method of/carbon composite, including with
Lower step:
Step one, 120g glucose are dissolved in 900mL deionized water, after stirring to clarify solution, are transferred to 1000mL hydro-thermal anti-
Answer in still, 220 DEG C, 900r/min rotating speed, hydro-thermal 4h, gained precursor solution by centrifugation, washing, after alcohol washes each 3 times, at 60 DEG C
Vacuum drying oven is dried 12h, prepares C ball；
Step 2, taking 5g dried C ball, 90 DEG C of heated and stirred 4h in 1000mL, 3M NaOH solution, then by mixture
After solution centrifugal, washing, alcohol wash each 3 times, 80 DEG C of vacuum drying ovens are dried 12h；Gained solid is calcined in argon gas atmosphere again
Processing, calcining heat is 900 DEG C, and calcination time is 1h；
Step 3, with the carbon ball after step 2 modification as template, be placed in the KMnO of 1000mL, 2.5g/L4In aqueous solution, room
Temperature stirring ageing 5h, is precipitated, and by pelleting centrifugation, after washing, alcohol wash each 3 times, is dried 12h in 60 DEG C of vacuum drying ovens,
To CS@MnO2Parcel powder.
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| CN105551813B (en) * | 2016-01-26 | 2018-08-21 | 华中科技大学 | A kind of MnO2The preparation method of/porous carbon membranes/nickel composite material |
| CN105869922A (en) * | 2016-04-11 | 2016-08-17 | 太原理工大学 | Rapid preparation method of manganese oxide/carbon sphere composite material for three-dimensional (3D) printing |
| CN106006755A (en) * | 2016-05-17 | 2016-10-12 | 山东大学 | Degradable magnetic nano material with caramel nanospheres as templates as well as preparation method and application of material in MRI (magnetic resonance imaging) |
| CN106517340A (en) * | 2016-12-12 | 2017-03-22 | 大连瑞源动力股份有限公司 | Method for inducing synthesis of spherical manganese carbonate |
| CN106927508B (en) * | 2017-03-08 | 2018-05-01 | 新乡学院 | A kind of cellular nano structure MnO2The preparation method of lithium ion battery anode material |
| CN106910646A (en) * | 2017-03-08 | 2017-06-30 | 新乡学院 | A kind of preparation method of ultracapacitor working electrode |
| CN109767925B (en) * | 2019-02-22 | 2020-09-15 | 扬州大学 | T-Nb for lithium ion super capacitor2O5Egg white carbon composite material and preparation method thereof |
| CN109888225A (en) * | 2019-02-27 | 2019-06-14 | 桑顿新能源科技有限公司 | Positive electrode and preparation method thereof and lithium ion battery |
| CN109950051B (en) * | 2019-04-28 | 2021-07-30 | 安徽大学 | Spherical core-shell structure C @ MnO2@ NiAl-LDH nano composite and preparation method thereof |
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