CN103413691A - Method for preparing MnO2/carbon composite material for super-capacitor - Google Patents

Method for preparing MnO2/carbon composite material for super-capacitor Download PDF

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CN103413691A
CN103413691A CN2013103295325A CN201310329532A CN103413691A CN 103413691 A CN103413691 A CN 103413691A CN 2013103295325 A CN2013103295325 A CN 2013103295325A CN 201310329532 A CN201310329532 A CN 201310329532A CN 103413691 A CN103413691 A CN 103413691A
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汪长安
李洒
李承书
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Tsinghua University
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Abstract

The invention provides a method for preparing a MnO2/carbon composite material for a super-capacitor. The method includes the steps of step one, dissolving glucose or sucrose or fructose in deionized water, stirring until a settled solution is obtained, transferring the settled solution into a hydrothermal reaction kettle, performing centrifugation, water washing, alcohol washing and drying on an obtained polymeric pecursor solution to prepare monodisperse carbon spheres; step two, taking the monodisperse carbon spheres, performing heat treatment on the monodisperse carbon spheres in a NaOH solution, then performing centrifugation, water washing and alcohol washing on a mixture solution three times, conducting drying, and performing calcination treatment in vacuum or inert atmosphere; step three, using the carbon spheres experiencing modified treatment in the step two as a template, placing the template in a KMnO4 aqueous solution, stirring and aging at the room temperature, obtaining a sediment, performing centrifugation, water washing and alcohol washing on the sediment, performing drying in a vacuum oven, and obtaining CS@MnO2 coated powder. Obtained MnO2/carbon sphere composite powder is of a core-shell structure, the specific surface area of the powder can reach more than 778m<2>/g, the specific capacity of the powder can reach more than 439F/g, charge transfer resistance is lower than 2.1 omega, and the powder is a novel super-capacitor electrode material.

Description

A kind of MnO for ultracapacitor 2The preparation method of/carbon composite
Technical field
The present invention relates to the new energy materials preparing technical field, particularly a kind of MnO for ultracapacitor 2The preparation method of/carbon composite.
Background technology
Ultracapacitor is as a kind of Novel energy storage apparatus, has to have extended cycle life, discharge and recharge that speed is fast, power is high and the characteristics such as environmentally friendly, therefore is subject to domestic and international scientist's extensive concern.The kind of ultracapacitor can be divided into double electric layer capacitor, Faraday pseudo-capacitance device by its operation principle.Double electric layer capacitor, based on the electric double layer theory, utilizes the interfacial electric double layer electric capacity formed between electrode and electrolyte to carry out storage power.The pseudo capacitance device is based on faraday's process, namely in the electrochemical change process that faraday's electric charge shifts, produce, do not occur over just electrode surface, and can go deep into electrode interior, therefore can obtain than the higher capacitance of double electric layer capacitor and energy density.
For developing the ultracapacitor of function admirable, having than the exploitation of the electrode material of height ratio capacity of vital exactly applicable supercapacitor applications, selected electrode material must easily form higher electric double layer capacitance or Faraday pseudo-capacitance on electrode/electrolyte interface, and have suitable mechanical stability, and good ion, electron conduction.Mainly concentrate at present the research of carbon-based material and transition metal oxide material.Wherein carbon-based material mainly utilizes the electric double layer capacitance amount that bigger serface produces, and macropore and mesoporously be conducive to reduce the potential polarization under high current density, and micropore helps increasing specific surface area, increases and compares electric capacity.In nearest research, to the research of metal oxide containing precious metals electrode capacitor, mainly adopt RuO 2, IrO 2Deng metal oxide containing precious metals as electrode material, due to RuO 2The conductivity of electrode is better than carbon electrode, and electrode is stable in sulfuric acid, can obtain higher specific energy, is a kind of electrode material of excellent performance, and the capacitor of preparation has better performance than carbon electrode capacitor, therefore has good development prospect.But, due to the resource-constrained of noble metal, the expensive use that has limited it.The oxide of transition metal series, many oxidation state due to metallic atom, outside under alive effect, can produce redox reaction fast greatly, from this basic principle, can predict, the oxide that is positioned at the transition metal zone element of the periodic table of elements all can have the fake capacitance performance similar to ruthenium-oxide.Prove after deliberation, manganese oxide all has supercapacitor properties preferably, and developing these substitutes is important developing direction.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, the object of the present invention is to provide a kind of MnO for ultracapacitor 2The preparation method of/carbon composite, be template with the synthetic dispersed nano carbon ball of hydro thermal method (Carbon sphere is called for short CS), passes through KMnO 4The redox reaction on solution and carbon ball surface forms MnO at carbon ball surface in situ 2Layer, control the size of carbon ball masterplate by hydrothermal condition, by carbon ball heat-treat condition, control the activity of its surface reduction group, by KMnO used 4Concentration, reaction temperature and reaction time condition are controlled the degree that redox reaction is carried out, and then reach control MnO 2The purpose of the relative scale of layer and the carbon ball heart, finally prepare MnO 2/ carbon ball composite structural ceramic powder; This powder product has possessed electric double layer capacitance and the MnO of porous carbon simultaneously 2Fake capacitance; In experimentation, by the adjusting to each synthesis condition, when acquisition has high-specific surface area, hierarchical porous structure, also make material have high specific capacity and low charge transfer resistance, to meet its application requirements on ultracapacitor.
In order to achieve the above object, technical scheme of the present invention is:
A kind of MnO for ultracapacitor 2The preparation method of/carbon composite comprises the following steps:
Step 1,60-120g glucose or sucrose or fructose are dissolved in the 900mL deionized water, after stirring to clarify solution, are transferred in the 1000mL hydrothermal reaction kettle; 150-250 ℃, 900r/min rotating speed, hydro-thermal 1-10h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 10-20h in 50-80 ℃ of vacuum drying oven, prepare single dispersed carbon ball;
Step 2, get the mono-dispersed carbon ball of 1-5g heat treated in 100-1000mL, 0.5M-5M concentrated NaOH solution, heating-up temperature is 50-90 ℃, be 0.5-12h heating time, then after mixture solution is centrifugal, washing, alcohol wash each 3 times, dry 10-20h in 50-80 ℃ of vacuum drying oven, the gained solid is calcination processing in vacuum or inert atmosphere again, and calcining heat is 300-1000 ℃, and calcination time is 0.5-5h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 100-1000mL, the KMnO of 2.5-25g/L 4In the aqueous solution, stirring at room ageing 0.5-5h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 10～20h, obtain CS@MnO in 50-80 ℃ of vacuum drying oven 2The parcel powder.
By above-mentioned technique, can obtain the MnO that specific area is large, higher than electric capacity, power density is high 2/ carbon ball composite ceramic material.
At first the present invention has prepared surperficial carbon ball with reproducibility oxygen-containing functional group, then by the later stage modification, improves carbon ball conductivity, reduces simultaneously its surface reduction.Recycle on this basis KMnO 4Strong oxidizing property and the reproducibility radical reaction on carbon ball surface, on the carbon ball deposition certain thickness MnO 2Layer, obtain MnO 2/ carbon ball composite construction.This special complex nucleus shell structure, as ultracapacitor the time, possesses electric double layer storage and the MnO of porous carbon simultaneously 2Faraday pseudo-capacitance mechanism, therefore have very high specific capacity.In addition, its electrically conductive core can reduce charge transfer resistance greatly, makes product have higher power density.Preparation technology of the present invention is simple, to material system require lowly, therefore be conducive to apply.
The present invention, according to the two kind mechanism of ultracapacitor at stored charge, designs a kind of MnO of nucleocapsid structure dexterously 2/ carbon ball composite material, it both can utilize the electric double layer principle stored charge of heart section porous carbon as electrode material for super capacitor the time, also can utilize outside MnO 2Faraday's principle stored charge that layer provides, thus very high specific capacity obtained.In addition, for further improving the power density of ultracapacitor, the present invention is at MnO 2Integument forms and front single dispersed carbon ball is carried out to modification, to improve the conductivity of powder, solves MnO 2Material is the excessive problem of resistance as super capacitor the time.Prepared MnO 2/ carbon ball composite granule presents nucleocapsid structure, and specific area can reach 778m 2More than/g, more than specific capacity reached 439F/g, charge transfer resistance, lower than 2.1 Ω, was a kind of novel electrode material for super capacitor.
The accompanying drawing explanation
Fig. 1 is the microstructure schematic diagram of single dispersed carbon ball template, and wherein Fig. 1 (a) is the SEM photo; Fig. 1 (b) is the TEM photo.
Fig. 2 is MnO 2The microstructure schematic diagram of/carbon ball composite structural ceramic powder, wherein Fig. 2 (a) is the SEM photo, Fig. 2 (b) TEM photo, Fig. 2 (c) BJH curve.
Fig. 3 (a) is product TEM partial enlarged drawing, Fig. 3 (b) is product TEM high-resolution photo, and Fig. 3 (c) is the product model, and Fig. 3 (d) is the cyclic voltammetry curve under different voltage scan rate, Fig. 3 (e) is the constant current charge-discharge curve, and Fig. 3 (f) is impedance spectrum.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
Embodiment mono-
The present embodiment comprises the following steps:
Step 1,60g sucrose is dissolved in the 900mL deionized water, after stirring to clarify solution, be transferred in the 1000mL hydrothermal reaction kettle, 150 ℃, 900r/min rotating speed, hydro-thermal 6h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare single dispersed carbon ball;
Step 2, get the mono-dispersed carbon ball of 1g heat treated in the NaOH of the 0.5M of 500mL solution, heating-up temperature is 50 ℃, be 12h heating time, then after mixture solution is centrifugal, washing, alcohol wash each 3 times, dry 12h in 50 ℃ of vacuum drying ovens, the gained solid is calcination processing in the argon gas atmosphere stove again, and calcining heat is 1000 ℃, and calcination time is 0.5h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 200mL, the KMnO of 5g/L 4In the aqueous solution, stirring at room ageing 5h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
From Fig. 1, can observe, prepared C ball template is better dispersed, and average diameter is 300nm.From Fig. 2, wrap up MnO 2After SEM photo and the TEM photo of carbon ball can find out, C ball surface becomes coarse, a lot of nanometer wire of surface attachment MnO 2, integument thickness is approximately 20nm.N 2About adsorption-desorption curve shows gained powder 3.4nm mesoporous, the porous carbon that this mainly comes from core, the specific area that calculates powder is 1032m 2/ g.Fig. 3 has reflected MnO 2Micro-structural feature and the capacitive property of/carbon ball composite structural ceramic powder, can find out MnO from the local TEM photo amplified Fig. 3 (a) 2Integument presents bar-shaped on the porous carbon ball, Fig. 3 (b) has reflected outer field MnO 2Crystallinity is fine, and this structure both had been conducive to ionic adsorption, desorption, also is conducive to the embedding of ion and extracts simultaneously, thereby improving the fake capacitance performance.According to Fig. 3 (a) and micro-structural feature (b), we have set up the functional mode of product as ultracapacitor the time, as shown in Fig. 3 (c) figure.In Fig. 3 (d), cyclic voltammetry curve presents symmetrical rectangle, is typical capacitive properties, while along with sweep speed, increasing to 75mv/s, and cyclic voltammetry curve rectangular shape variation.This is because when low sweep speed, the electronics in solution can with carbon ball and MnO 2Layer is contact fully, and reversible reaction occurs; But when too high sweep speed, the electronics of electrode surface has little time reaction, be equivalent to resistance and increase, cause the electrode charge and discharge hydraulic performance decline, so its cyclic voltammetry curve shape changes.We can find that in 0～0.9V scope, charging curve and discharge curve have comparatively ideal symmetry, and MnO is described by the constant current charge-discharge curve in Fig. 3 (e) 2/ carbon ball composite structural ceramic powder carries out in electrolyte solution oxidation reaction and reduction reaction are reversible, by calculating MnO 2The specific capacity of/carbon ball composite structural ceramic powder reaches 583F/g.By Fig. 3 (f) middle impedance, composed the data of high frequency region and know, in solution electrode, charge transfer resistance is 1.2 Ω, illustrates that heart section carbon ball has extraordinary conductivity.Therefore this material can be used as a kind of super capacitor material of novel high-performance.
Embodiment bis-
The present embodiment comprises the following steps:
Step 1,80g fructose is dissolved in the 900mL deionized water, after stirring to clarify solution, be transferred in the 1000mL hydrothermal reaction kettle, 170 ℃, 900r/min rotating speed, hydro-thermal 3h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare single dispersed carbon ball;
Step 2, get the mono-dispersed carbon ball of 1.5g heat treated in the 2M of 200mL NaOH solution, heating-up temperature is 70 ℃, be 8h heating time, then after mixture solution is centrifugal, washing, alcohol wash each 3 times, dry 15h in 60 ℃ of vacuum drying ovens, the gained solid is again in the vacuum furnace calcination processing, and calcining heat is 700 ℃, and calcination time is 2h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 500mL, the KMnO of 10g/L 4In the aqueous solution, stirring at room ageing 4h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
The measurement powder specific-surface area detection is 974m 2/ g, specific capacity is 557F/g, charge transfer resistance is 1.0 Ω.
Embodiment tri-
The present embodiment comprises the following steps:
Step 1,100g glucose are dissolved in the 900mL deionized water, after stirring to clarify solution, are transferred in the 1000mL hydrothermal reaction kettle 200 ℃, 900r/min rotating speed, hydro-thermal 3h; The gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare the C ball.
Step 2, get the dried C ball of 3g, 80 ℃ add thermal agitation 6h in 750mL, 5M NaOH solution, after then mixture solution is centrifugal, washing, alcohol wash each 3 times, and dry 12h in 80 ℃ of vacuum drying ovens.The gained solid is calcination processing in argon gas atmosphere again, and calcining heat is 800 ℃, and calcination time is 2h.
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 800mL, the KMnO of 15g/L 4In the aqueous solution, stirring at room ageing 1h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
The measurement powder specific-surface area detection is 902m 2/ g, specific capacity is 495F/g, charge transfer resistance is 1.4 Ω.
Embodiment tetra-
The present embodiment comprises the following steps:
Step 1,120g glucose are dissolved in the 900mL deionized water, after stirring to clarify solution, are transferred in the 1000mL hydrothermal reaction kettle 220 ℃, 900r/min rotating speed, hydro-thermal 4h; The gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare the C ball;
Step 2, get the dried C ball of 5g, 90 ℃ add thermal agitation 4h in 1000mL, 3M NaOH solution, after then mixture solution is centrifugal, washing, alcohol wash each 3 times, and dry 12h in 80 ℃ of vacuum drying ovens.The gained solid is calcination processing in argon gas atmosphere again, and calcining heat is 900 ℃, and calcination time is 1h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 1000mL, the KMnO of 2.5g/L 4In the aqueous solution, stirring at room ageing 5h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
The measurement powder specific-surface area detection is 778m 2/ g, specific capacity is 439F/g, charge transfer resistance is 2.1 Ω.

Claims (5)

1. MnO for ultracapacitor 2The preparation method of/carbon composite comprises the following steps:
Step 1,60-120g glucose or sucrose or fructose are dissolved in the 900mL deionized water, after stirring to clarify solution, are transferred in the 1000mL hydrothermal reaction kettle; 150-250 ℃, 900r/min rotating speed, hydro-thermal 1-10h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 10-20h in 50-80 ℃ of vacuum drying oven, prepare single dispersed carbon ball;
Step 2, get the mono-dispersed carbon ball of 1-5g heat treated in 100-1000mL, 0.5M-5M concentrated NaOH solution, heating-up temperature is 50-90 ℃, be 0.5-12h heating time, then after mixture solution is centrifugal, washing, alcohol wash each 3 times, dry 10-20h in 50-80 ℃ of vacuum drying oven, the gained solid is calcination processing in vacuum or inert atmosphere again, and calcining heat is 300-1000 ℃, and calcination time is 0.5-5h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 100-1000mL, the KMnO of 2.5-25g/L 4In the aqueous solution, stirring at room ageing 0.5-5h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 10～20h, obtain CS@MnO in 50-80 ℃ of vacuum drying oven 2The parcel powder.
2. a kind of MnO for ultracapacitor according to claim 1 2The preparation method of/carbon composite comprises the following steps:
Step 1,60g sucrose is dissolved in the 900mL deionized water, after stirring to clarify solution, be transferred in the 1000mL hydrothermal reaction kettle, 150 ℃, 900r/min rotating speed, hydro-thermal 6h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare single dispersed carbon ball;
Step 2, get the mono-dispersed carbon ball of 1g heat treated in the NaOH of the 0.5M of 500mL solution, heating-up temperature is 50 ℃, be 12h heating time, then after mixture solution is centrifugal, washing, alcohol wash each 3 times, dry 12h in 50 ℃ of vacuum drying ovens, the gained solid is calcination processing in the argon gas atmosphere stove again, and calcining heat is 1000 ℃, and calcination time is 0.5h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 200mL, the KMnO of 5g/L 4In the aqueous solution, stirring at room ageing 5h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
3. a kind of MnO for ultracapacitor according to claim 1 2The preparation method of/carbon composite comprises the following steps:
Step 1,80g fructose is dissolved in the 900mL deionized water, after stirring to clarify solution, be transferred in the 1000mL hydrothermal reaction kettle, 170 ℃, 900r/min rotating speed, hydro-thermal 3h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare single dispersed carbon ball;
Step 2, get the mono-dispersed carbon ball of 1.5g heat treated in the 2M of 200mL NaOH solution, heating-up temperature is 70 ℃, be 8h heating time, then after mixture solution is centrifugal, washing, alcohol wash each 3 times, dry 15h in 60 ℃ of vacuum drying ovens, the gained solid is again in the vacuum furnace calcination processing, and calcining heat is 700 ℃, and calcination time is 2h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 500mL, the KMnO of 10g/L 4In the aqueous solution, stirring at room ageing 4h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
4. a kind of MnO for ultracapacitor according to claim 1 2The preparation method of/carbon composite comprises the following steps:
Step 1,100g glucose are dissolved in the 900mL deionized water, after stirring to clarify solution, be transferred in the 1000mL hydrothermal reaction kettle, 200 ℃, 900r/min rotating speed, hydro-thermal 3h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare the C ball;
Step 2, get the dried C ball of 3g, 80 ℃ add thermal agitation 6h in 750mL, 5M NaOH solution, after then mixture solution is centrifugal, washing, alcohol wash each 3 times, and dry 12h in 80 ℃ of vacuum drying ovens; The gained solid is calcination processing in argon gas atmosphere again, and calcining heat is 800 ℃, and calcination time is 2h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 800mL, the KMnO of 15g/L 4In the aqueous solution, stirring at room ageing 1h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
5. a kind of MnO for ultracapacitor according to claim 1 2The preparation method of/carbon composite comprises the following steps:
Step 1,120g glucose are dissolved in the 900mL deionized water, after stirring to clarify solution, be transferred in the 1000mL hydrothermal reaction kettle, 220 ℃, 900r/min rotating speed, hydro-thermal 4h, the gained precursor solution is after centrifugal, washing, alcohol wash each 3 times, and dry 12h in 60 ℃ of vacuum drying ovens, prepare the C ball;
Step 2, get the dried C ball of 5g, 90 ℃ add thermal agitation 4h in 1000mL, 3M NaOH solution, after then mixture solution is centrifugal, washing, alcohol wash each 3 times, and dry 12h in 80 ℃ of vacuum drying ovens.The gained solid is calcination processing in argon gas atmosphere again, and calcining heat is 900 ℃, and calcination time is 1h;
Step 3, the carbon ball of take after the step 2 modification are template, are placed in 1000mL, the KMnO of 2.5g/L 4In the aqueous solution, stirring at room ageing 5h, be precipitated, will precipitate centrifugal, washing, alcohol wash each after 3 times, dry 12h in 60 ℃ of vacuum drying ovens, obtain CS@MnO 2The parcel powder.
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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)
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