CN105280393A - Amorphous carbon material for nano tunnel and preparation method thereof - Google Patents
Amorphous carbon material for nano tunnel and preparation method thereof Download PDFInfo
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- CN105280393A CN105280393A CN201510824176.3A CN201510824176A CN105280393A CN 105280393 A CN105280393 A CN 105280393A CN 201510824176 A CN201510824176 A CN 201510824176A CN 105280393 A CN105280393 A CN 105280393A
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses an amorphous carbon material for a nano tunnel and a preparation method thereof. The preparation method comprises: first, preparing nano-rod-shaped manganese dioxide by reducing potassium permanganate under hydrothermal conditions; then, evenly mixing the nano-rod-shaped manganese dioxide with biomass carbon precursor using the nano-rod-shaped manganese dioxide as template to obtain a stable hydrogel; then, performing vacuum drying and carbonization for the hydrogel; finally, removing the manganese dioxide from the carbon material with acid and performing further activation to obtain the amorphous carbon material for the nano tunnel. The amorphous carbon material for the nano tunnel prepared by the method has high specific surface area and porosity. At the same time, the liquid phase diffusion of ions can be achieved in the tunnel; the diffusion speed of ions is greatly increased; the resistance of mass transfer is reduced; and the electrochemical capacitance performance of electrode materials is increased. The beneficial effects of the amorphous carbon material for the nano tunnel used as super capacitor electrode materials are: high specific capacity, long cycle life and high specific energy.
Description
Technical field
The present invention relates to material science and field of chemical power source, specifically, amorphous carbon material relating to a kind of nano tunnel and preparation method thereof.
Background technology
Ultracapacitor is a kind of novel energy storage device between secondary cell and traditional capacitor, has the advantage that secondary cell energy density is large and traditional capacitor power density is high simultaneously.In addition, ultracapacitor also have have extended cycle life, security performance is good, the advantages such as environmental pollution is little.It is with a wide range of applications in New-energy electric vehicle, information technology, defence and military and some miniaturized electronicss etc.According to different charge storage mechanisms, ultracapacitor can divide double electric layers supercapacitor and fake capacitance ultracapacitor.At present, commercialization ultracapacitor is mainly based on double electric layer capacitor.The electric double layer that double electric layer capacitor mainly utilizes electrode and electrolyte interface to be formed carrys out storage power, its electrode material mainly Carbon Materials.
Carbon Materials, because having stable cycle life, higher specific area and cheap price, has been widely used in business-like ultracapacitor.The microstructure of Carbon Materials and the specific capacity relation complexity of ultracapacitor.More Large Copacity can be higher to think the specific area of Carbon Materials in theory, but in fact specific capacity is also relevant with the pore-size distribution of material, internal resistance and surface functional group etc.Many researchers are to the transmission of Carbon Materials grading-hole intermediate ion and storage (DWWangetal, Angew.Chem.Int.Ed., 2008,47:373-376), the energy storage model (RMysyketal in secondary nano-pore, Electrochem.Commun., 2009,11:554-556) with aperture coupling (LWangetal, Electrochim.Acta, 2007,53:882-886) etc. in electric double layer energy storage, theoretical question is studied, thus provides good directive significance for the preparation of Carbon Materials and structure optimization.Desirable Carbon Materials should have high specific area, high bulk density, high porosity and high cost performance simultaneously.The patent No. be 201010277238.0 patent discloses a kind of glucose and blowing agent first prepares hemispherical active carbon by the method for hydro thermal method process, again high temperature cabonization, experimental procedure is simple, and reaction condition is gentleer.Carbon Materials specific area can reach 851.75m
2g
-1, when current density is 20mAcm
-2time, ratio capacitance is 267.83Fg
-1.The patent No. be 200510031195.7 patent a kind of preparation method of active carbon with high specific surface area is disclosed, with stone tar for raw material and KOH mixing carbonization, the active carbon specific area prepared is at 2000 ~ 3000m
2g
-1between, but ratio capacitance only has 84Fg
-1.
In the present invention, by utilizing nano bar-shape manganese dioxide as template, synthesize a kind of amorphous microporous charcoal with nano tunnel.Material has high specific surface area and porosity.Because the width of nano tunnel is between 20 ~ 80nm, length, between 0.2 ~ 3 μm, illustrates that to there are some in the material mesoporous.After chemical activation, can there is many micropores in Carbon Materials.Can liquid phase diffusion be carried out at nano tunnel intermediate ion, substantially increase ion diffuse speed, reduce mass transfer impedance, make ion more easily arrive micropore, improve the utilance of micropore.The existence of micropore is beneficial to the absorption of ion, thus forms stable electric double layer.The Carbon Materials of the method synthesis not only has good electrochemical capacitor performance, the more important thing is this Measures compare environmental protection, cheapness and safety.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, amorphous carbon material that a kind of nano tunnel is provided and preparation method thereof, be applied in ultracapacitor, due to the structural particularity of nano tunnel Microporous Carbon, thus improve specific capacity and the specific energy of ultracapacitor.
An amorphous carbon material for nano tunnel, is prepared from by the following method:
(1) under the condition of hydro-thermal, reduce potassium permanganate, prepare nano bar-shape manganese dioxide;
(2) by the manganese dioxide powder ultrasonic disperse that obtains in step (1) in deionized water, uniform suspension is formed; Get biomass carbon precursor and surfactant dissolves again in water, form stable mixed solution; Under the condition of uniform temperature and stirring, manganese dioxide suspension is dropwise added in the mixed solution of biomass carbon presoma and surfactant, and constant temperature stirs, and when mixed solution cool to room temperature, forms stable sepia hydrogel;
(3) by after the hydrogel vacuumize that obtains in step (2), transfer in porcelain boat; In tube furnace, under inert gas shielding condition, carry out carbonization; With the manganese dioxide in acid removing Carbon Materials after carbonization, then spend deionized water several times, then dry;
(4) product in step (3) and activator mix is even, then at high temperature carry out the amorphous carbon material that chemical activation obtains nano tunnel.
Preferably, in described step (1), the condition of reduction potassium permanganate is as follows: hydrothermal temperature is between 120 ~ 200 DEG C, and the hydro-thermal time is 1 ~ 20h; Reducing agent used is MnCl
2, MnSO
4or the one in HCl; The mol ratio of potassium permanganate and reducing agent is between 1:1 ~ 1:20.
Preferably, in described step (2), the mass concentration of manganese dioxide is 1gL
-1~ 20gL
-1, biomass carbon presoma is the one in glucose, agar, shitosan, sugarcane sugar and starch, and its mass concentration is 20gL
-1~ 50gL
-1; Surfactant is the one in polyvinyl alcohol, CMC and cyclodextrin, and its mass concentration is 1gL
-1~ 10gL
-1.
Preferably, in described step (2), when temperature is 40 ~ 80 DEG C, dropwise added by manganese dioxide suspension in the mixed solution of biomass carbon presoma and surfactant, drop rate is per minute at 60 ~ 120; After both mix, at 40 ~ 80 DEG C, stir 2 ~ 12h.Last cool to room temperature, obtains stable sepia hydrogel.
Preferably, in described step (3), the vacuum drying condition of hydrogel is as follows: baking temperature is between 40 ~ 80 DEG C, and drying time is 5 ~ 24h.
Preferably, in described step (3), Carbonization Conditions is as follows: under an inert atmosphere, by dried hydrogel first at 200 ~ 400 DEG C, constant temperature 1 ~ 3h, subsequently carbonization 1 ~ 3h at 600 ~ 900 DEG C, heating rate is 2 ~ 5 DEG C of min
-1.
Preferably, in described step (3), the condition of removing manganese dioxide is as follows: by the product cool to room temperature obtained after carbonization, with the manganese dioxide in acid elution removing material; Acid used is the one in hydrochloric acid, oxalic acid, sulfuric acid, and concentration is at 0.1molL
-1~ 2molL
-1between.
Preferably, the activation condition in described step (4) is as follows: the activator selected is H
3pO
3, ZnCl
2, one in KOH, the mass ratio of Carbon Materials and activator is between 1:1 ~ 1:4, and activation temperature is between 500 ~ 800 DEG C.
A kind of electrode material for super capacitor, electrode material comprises above-mentioned nano tunnel amorphous carbon material, binding agent and conductive agent; Wherein: the quality of nano tunnel amorphous carbon material is 80% of electrode material gross mass, and the quality of binding agent is 10% of electrode material gross mass, and the quality of conductive agent is 10% of electrode material gross mass.
The preparation method of above-mentioned electrode material for super capacitor: slurry deployed for the material of said ratio is coated on stainless (steel) wire collector, or be coated on aluminium foil; The quality of the electrode active material obtained after drying is 1 ~ 3mg.
By the electrode for preparing at 60 DEG C of vacuumize 12h, at 1MH
2sO
4electro-chemical test is carried out in electrolyte.Pt and Hg/Hg
2sO
4be respectively electrode and reference electrode.Be-0.5 ~ 0.3V at electrochemical window, sweep speed for 100mVs
-1under carry out cyclic voltammetry, and calculate specific capacity.The electrode slice prepared is assembled into symmetric form ultracapacitor, and electrolyte is dicyclo fourth ammonium four villiaumites/acetonitrile, is 0 ~ 3V at electrochemical window, and current density is 1Ag
-1lower test, and calculate specific capacity and specific energy.
Compared with prior art, the present invention has following beneficial effect: the preparation-obtained Carbon Materials of the present invention is amorphous active carbon, and it contains many crisscross nano tunnel, and width is between 20 ~ 80nm, and length is 0.2 ~ 3 μm; Further, this Carbon Materials has high-specific surface area (>1200m
2g
-1), material has micropore and mesoporous character simultaneously.Experiment condition of the present invention is gentleer; Manganese dioxide nano-rod is easy to acid removing, and leaves a lot of nano tunnel in Carbon Materials inside; Experimental technique safety, environmental protection and cheapness.
Accompanying drawing explanation
Fig. 1 is the picture of hydrogel in the present invention;
Fig. 2 is the transmission electron microscope picture of manganese dioxide nano-rod in the present invention;
Fig. 3 is the transmission electron microscope picture of nano tunnel Microporous Carbon of the present invention;
Cyclic voltammogram when Fig. 4 is nano tunnel Carbon Materials three electrode test of embodiment 1 preparation in the present invention.
Embodiment
embodiment 1:
A. the MnO of nano bar-shape
2preparation: get 20gKMnO
4be dissolved in 1L water, then add 15mlHCl, stir, transfer in hydrothermal reaction kettle, constant temperature 16h at 140 DEG C.Cool to room temperature, spends deionized water three times, then puts into the dry 24h of air dry oven, obtains the MnO of nano bar-shape
2powder.
B. the preparation of nano tunnel micropore carbon material: get 10gMnO
2ultrasonic disperse is in 1L deionized water.Get 20g agar stirring and dissolving under 70 DEG C of conditions, in 1L deionized water, to add 5g CMC and stir.Under 70 DEG C of conditions stirred, by MnO
2suspension is added drop-wise in agar and CMC mixed solution with the speed of 60 per minute, then continues to stir 2h under 70 DEG C of conditions.Cool to room temperature, obtains uniform and stable sepia hydrogel.Hydrogel, after 60 DEG C of vacuumize 12h, is transferred in porcelain boat, with 3 DEG C of min
-1heating rate to 300 DEG C of constant temperature 2h again to 800 DEG C of constant temperature 2h.During cool to room temperature, remove the MnO in Carbon Materials with 1MHCl
2, then spend deionized water three times.Finally dried Carbon Materials is mixed with the mass ratio of 1:2 with KOH, at 700 DEG C, activate 1h.Use washed with de-ionized water four times after cooling, drying obtains the Microporous Carbon of nano tunnel.
C. electro-chemical test: (three electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be coated on stainless (steel) wire, carry out electro-chemical test after 60 DEG C of vacuumize 12h.1MH selected by electrolyte
2sO
4, be-0.5 ~ 0.3V at electrochemical window, sweep speed for 100mVs
-1shi Jinhang cyclic voltammetry, specific capacity is 200Fg
-1.(two electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be uniformly coated on aluminium foil, 60 DEG C of vacuumize, roll, cut into slices, in glove box, be assembled into symmetric form ultracapacitor.Electrolyte is dicyclo fourth ammonium four villiaumites/acetonitrile, carries out constant current charge-discharge test when electrochemical window is 0 ~ 3V, when current density is 1Ag
-1time specific energy up to 31Whkg
-1.
embodiment 2:
A. the MnO of nano bar-shape
2preparation: get 20gKMnO
4be dissolved in 1L water, then add 15mlHCl, stir, transfer in autoclave, constant temperature 16h at 140 DEG C.Cool to room temperature, spends deionized water three times, then puts into the dry 24h of air dry oven, obtains the MnO of nano bar-shape
2powder.
b.the preparation of nano tunnel micropore carbon material: get 10gMnO
2ultrasonic disperse is in 1L deionized water.Get 20g starch stirring and dissolving under 70 DEG C of conditions, in 1L deionized water, to add 5g CMC and stir.Under 70 DEG C of conditions stirred, by MnO
2suspension is added drop-wise in starch and CMC mixed solution with the speed of 60 per minute, then continues to stir 2h under 70 DEG C of conditions.Cool to room temperature, obtains uniform and stable sepia hydrogel.Hydrogel, after 60 DEG C of vacuumize 12h, is transferred in porcelain boat, with 3 DEG C of min
-1heating rate to 300 DEG C of constant temperature 2h again to 800 DEG C of constant temperature 2h.During cool to room temperature, remove the MnO in Carbon Materials with 1MHCl
2, then spend deionized water three times.Finally dried Carbon Materials is mixed with the mass ratio of 1:2 with KOH, at 700 DEG C, activate 1h.Use washed with de-ionized water four times after cooling, drying obtains the Microporous Carbon of nano tunnel.
c.electro-chemical test: (three electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be coated on stainless (steel) wire, carry out electro-chemical test after 60 DEG C of vacuumize 12h.1MH selected by electrolyte
2sO
4, be-0.5 ~ 0.3V at electrochemical window, sweep speed for 100mVs
-1shi Jinhang cyclic voltammetry, specific capacity is 196Fg
-1.(two electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be uniformly coated on aluminium foil, 60 DEG C of vacuumize, roll, cut into slices, in glove box, be assembled into symmetric form ultracapacitor.Electrolyte is dicyclo fourth ammonium four villiaumites/acetonitrile, carries out constant current charge-discharge test when electrochemical window is 0 ~ 3V, when current density is 1Ag
-1time specific energy up to 29Whkg
-1.
embodiment 3:
A. the MnO of nano bar-shape
2preparation: get 20gKMnO
4be dissolved in 1L water, then add 15mlHCl, stir, transfer in autoclave, constant temperature 16h at 140 DEG C.Cool to room temperature, spends deionized water three times, then puts into the dry 24h of air dry oven, obtains the MnO of nano bar-shape
2powder.
B. the preparation of nano tunnel micropore carbon material: get 10gMnO
2ultrasonic disperse is in 1L deionized water.Get 40g agar stirring and dissolving under 70 DEG C of conditions, in 1L deionized water, to add 5g CMC and stir.Under 70 DEG C of conditions stirred, by MnO
2suspension is added drop-wise in agar and CMC mixed solution with the speed of 60 per minute, then continues to stir 2h under 70 DEG C of conditions.Cool to room temperature, obtains uniform and stable sepia hydrogel.Hydrogel, after 60 DEG C of vacuumize 12h, is transferred in porcelain boat, with 3 DEG C of min
-1heating rate to 300 DEG C of constant temperature 2h again to 800 DEG C of constant temperature 2h.During cool to room temperature, remove the MnO in Carbon Materials with 1MHCl
2, then spend deionized water three times.Finally dried Carbon Materials is mixed with the mass ratio of 1:2 with KOH, at 700 DEG C, activate 1h.Use washed with de-ionized water four times after cooling, drying obtains the Microporous Carbon of nano tunnel.
C. electro-chemical test: (three electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be coated on stainless (steel) wire, carry out electro-chemical test after 60 DEG C of vacuumize 12h.1MH selected by electrolyte
2sO
4, be-0.5 ~ 0.3V at electrochemical window, sweep speed for 100mVs
-1shi Jinhang cyclic voltammetry, specific capacity is 167Fg
-1.(two electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be uniformly coated on aluminium foil, 60 DEG C of vacuumize, roll, cut into slices, in glove box, be assembled into symmetric form ultracapacitor.Electrolyte is dicyclo fourth ammonium four villiaumites/acetonitrile, carries out constant current charge-discharge test when electrochemical window is 0 ~ 3V, when current density is 1Ag
-1time specific energy up to 21Whkg
-1.
embodiment 4:
A. the MnO of nano bar-shape
2preparation: get 20gKMnO
4be dissolved in 1L water, then add 15mlHCl, stir, transfer in autoclave, constant temperature 16h at 140 DEG C.Cool to room temperature, spends deionized water three times, then puts into the dry 24h of air dry oven, obtains the MnO of nano bar-shape
2powder.
B. the preparation of nano tunnel micropore carbon material: get 10gMnO
2ultrasonic disperse is in 1L deionized water.Get 20g agar stirring and dissolving under 70 DEG C of conditions, in 1L deionized water, to add 5g cyclodextrin and stir.Under 70 DEG C of conditions stirred, by MnO
2suspension is added drop-wise in agar and cyclodextrin mixed solution with the speed of 60 per minute, then continues to stir 2h under 70 DEG C of conditions.Cool to room temperature, obtains uniform and stable sepia hydrogel.Hydrogel, after 60 DEG C of vacuumize 12h, is transferred in porcelain Noah's ark, with 3 DEG C of min
-1heating rate to 300 DEG C of constant temperature 2h again to 800 DEG C of constant temperature 2h.During cool to room temperature, remove the MnO in Carbon Materials with 1MHCl
2, then spend deionized water three times.Finally dried Carbon Materials is mixed with the mass ratio of 1:2 with KOH, at 700 DEG C, activate 1h.Use washed with de-ionized water four times after cooling, drying obtains the Microporous Carbon of nano tunnel.
C. electro-chemical test: electro-chemical test: (three electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, add nitrogen methyl pyrrolidone to size mixing, be coated on stainless (steel) wire, after 60 DEG C of vacuumize 12h, carry out electro-chemical test.1MH selected by electrolyte
2sO
4, be-0.5 ~ 0.3V at electrochemical window, sweep speed for 100mVs
-1shi Jinhang cyclic voltammetry, specific capacity is 215Fg
-1.(two electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be uniformly coated on aluminium foil, 60 DEG C of vacuumize, roll, cut into slices, in glove box, be assembled into symmetric form ultracapacitor.Electrolyte is dicyclo fourth ammonium four villiaumites/acetonitrile, carries out constant current charge-discharge test when electrochemical window is 0 ~ 3V, when current density is 1Ag
-1time specific energy up to 33Whkg
-1.
embodiment 5:
A. the MnO of nano bar-shape
2preparation: get 20gKMnO
4be dissolved in 1L water, then add 15mlHCl, stir, transfer in autoclave, constant temperature 16h at 140 DEG C.Cool to room temperature, spends deionized water three times, then puts into the dry 24h of air dry oven, obtains the MnO of nano bar-shape
2powder.
B. the preparation of nano tunnel micropore carbon material: get 10gMnO
2ultrasonic disperse is in 1L deionized water.Get 20g agar stirring and dissolving under 70 DEG C of conditions, in 1L deionized water, to add 5g CMC and stir.Under 70 DEG C of conditions stirred, by MnO
2suspension is added drop-wise in agar and CMC mixed solution with the speed of 60 per minute, then continues to stir 2h under 70 DEG C of conditions.Cool to room temperature, obtains uniform and stable sepia hydrogel.Hydrogel, after 60 DEG C of vacuumize 12h, is transferred in porcelain Noah's ark, with 3 DEG C of min
-1heating rate to 300 DEG C of constant temperature 2h again to 600 DEG C of constant temperature 2h.During cool to room temperature, remove the MnO in Carbon Materials with 1MHCl
2, then spend deionized water three times.Finally dried Carbon Materials is mixed with the mass ratio of 1:2 with KOH, at 700 DEG C, activate 1h.Use washed with de-ionized water four times after cooling, drying obtains the Microporous Carbon of nano tunnel.
C. electro-chemical test: (three electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be coated on stainless (steel) wire, carry out electro-chemical test after 60 DEG C of vacuumize 12h.1MH selected by electrolyte
2sO
4, be-0.5 ~ 0.3V at electrochemical window, sweep speed for 100mVs
-1shi Jinhang cyclic voltammetry, specific capacity is 183Fg
-1.(two electrodes) gets nano tunnel Microporous Carbon, acetylene black and the PVDF that mass ratio is 80:10:10, grinding evenly, adds nitrogen methyl pyrrolidone and sizes mixing, be uniformly coated on aluminium foil, 60 DEG C of vacuumize, roll, cut into slices, in glove box, be assembled into symmetric form ultracapacitor.Electrolyte is dicyclo fourth ammonium four villiaumites/acetonitrile, carries out constant current charge-discharge test when electrochemical window is 0 ~ 3V, when current density is 1Ag
-1time specific energy up to 26Whkg
-1.
Claims (10)
1. an amorphous carbon material for nano tunnel, is characterized in that being prepared from by the following method:
Under the condition of hydro-thermal, reduce potassium permanganate, prepare nano bar-shape manganese dioxide;
By the manganese dioxide powder ultrasonic disperse that obtains in step (1) in deionized water, uniform suspension is formed; Get biomass carbon precursor and surfactant dissolves again in water, form stable mixed solution; Under the condition of uniform temperature and stirring, manganese dioxide suspension is dropwise added in the mixed solution of biomass carbon presoma and surfactant, and constant temperature stirs, and when mixed solution cool to room temperature, forms stable sepia hydrogel;
By after the hydrogel vacuumize that obtains in step (2), transfer in porcelain boat; In tube furnace, under inert gas shielding condition, carry out carbonization; With the manganese dioxide in acid removing Carbon Materials after carbonization, then spend deionized water several times, then dry;
Product in step (3) and activator mix is even, then at high temperature carry out the amorphous carbon material that chemical activation obtains nano tunnel.
2. the amorphous carbon material of nano tunnel according to claim 1, is characterized in that the condition of reduction potassium permanganate in described step (1) is as follows: hydrothermal temperature is between 120 ~ 200 DEG C, and the hydro-thermal time is 1 ~ 20h; Reducing agent used is MnCl
2, MnSO
4or the one in HCl; The mol ratio of potassium permanganate and reducing agent is between 1:1 ~ 1:20.
3. the amorphous carbon material of nano tunnel according to claim 1, is characterized in that in described step (2), and the mass concentration of manganese dioxide is 1gL
-1~ 20gL
-1, biomass carbon presoma is the one in glucose, agar, shitosan, sugarcane sugar and starch, and its mass concentration is 20gL
-1~ 50gL
-1; Surfactant is the one in polyvinyl alcohol, CMC and cyclodextrin, and its mass concentration is 1gL
-1~ 10gL
-1.
4. the amorphous carbon material of nano tunnel according to claim 1, it is characterized in that in described step (2), when temperature is 40 ~ 80 DEG C, dropwise added by manganese dioxide suspension in the mixed solution of biomass carbon presoma and surfactant, drop rate is per minute at 60 ~ 120; After both mix, at 40 ~ 80 DEG C, stir 2 ~ 12h; Last cool to room temperature, obtains stable sepia hydrogel.
5. the amorphous carbon material of nano tunnel according to claim 1, is characterized in that in described step (3), the vacuum drying condition of hydrogel is as follows: baking temperature is between 40 ~ 80 DEG C, and drying time is 5 ~ 24h.
6. the amorphous carbon material of nano tunnel according to claim 1, it is characterized in that in described step (3), Carbonization Conditions is as follows: under an inert atmosphere, by dried hydrogel first at 200 ~ 400 DEG C, constant temperature 1 ~ 3h, carbonization 1 ~ 3h at 600 ~ 900 DEG C subsequently, heating rate is 2 ~ 5 DEG C of min
-1.
7. the amorphous carbon material of nano tunnel according to claim 1, is characterized in that the condition of removing manganese dioxide in described step (3) is as follows: by the product cool to room temperature obtained after carbonization, with the manganese dioxide in acid elution removing material; Acid used is the one in hydrochloric acid, oxalic acid, sulfuric acid, and concentration is at 0.1molL
-1~ 2molL
-1between.
8. the amorphous carbon material of nano tunnel according to claim 1, is characterized in that the activation condition in described step (4) is as follows: the activator selected is H
3pO
3, ZnCl
2, one in KOH, the mass ratio of Carbon Materials and activator is between 1:1 ~ 1:4, and activation temperature is between 500 ~ 800 DEG C.
9. an electrode material for super capacitor, is characterized in that, electrode material comprises nano tunnel amorphous carbon material, binding agent and conductive agent described in claim 1-8; Wherein: the quality of nano tunnel amorphous carbon material is 80% of electrode material gross mass, and the quality of binding agent is 10% of electrode material gross mass, and the quality of conductive agent is 10% of electrode material gross mass.
10. the preparation method of electrode material for super capacitor described in claim 9, is characterized in that, is coated on stainless (steel) wire collector by slurry deployed for the material of said ratio, or is coated on aluminium foil; The quality of the electrode active material obtained after drying is 1 ~ 3mg.
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| CN103594254A (en) * | 2013-11-26 | 2014-02-19 | 华东理工大学 | Method for preparing manganese dioxide/mesoporous carbon nanometer graded composite electrode material |
| CN104538199A (en) * | 2014-12-03 | 2015-04-22 | 浙江大学 | Preparation method of manganese oxide/porous carbon nanofiber composite material and product and application thereof |
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| KR20120032286A (en) * | 2010-09-28 | 2012-04-05 | 고려대학교 산학협력단 | Supercatpacitor electrode based on mno2/cnt/papers and the synthesis of the electrode |
| CN102664107A (en) * | 2012-05-31 | 2012-09-12 | 北京科技大学 | Preparation method of nano-manganese dioxide electrode |
| CN103545122A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Preparation method for manganese dioxide/carbon composite materials used for super capacitor |
| CN103594254A (en) * | 2013-11-26 | 2014-02-19 | 华东理工大学 | Method for preparing manganese dioxide/mesoporous carbon nanometer graded composite electrode material |
| CN104538199A (en) * | 2014-12-03 | 2015-04-22 | 浙江大学 | Preparation method of manganese oxide/porous carbon nanofiber composite material and product and application thereof |
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| CN107585783A (en) * | 2016-07-08 | 2018-01-16 | 中国科学院金属研究所 | A kind of tin oxide nano tube self-assembled film material and preparation method thereof and arsenic removal application |
| CN107585783B (en) * | 2016-07-08 | 2019-11-26 | 中国科学院金属研究所 | A kind of tin oxide nano tube self-assembled film material and preparation method thereof and arsenic removal application |
| CN108630439A (en) * | 2018-03-09 | 2018-10-09 | 华南师范大学 | A kind of preparation method of spherical shape carbon coating manganese dioxide nano-composite material |
| CN110416559A (en) * | 2018-04-26 | 2019-11-05 | 天津大学 | A kind of support type calcium manganese oxide composite material and its preparation method and application |
| CN110416560A (en) * | 2018-04-26 | 2019-11-05 | 天津大学 | A kind of calcium Mn oxide material and its preparation method and application |
| CN110416560B (en) * | 2018-04-26 | 2022-05-20 | 天津大学 | Calcium manganese oxide material and preparation method and application thereof |
| CN109179554A (en) * | 2018-10-10 | 2019-01-11 | 湖南大学 | Utilize the method for fortimicin in manganese dioxide load biological carbon materials removal water body |
| CN109796048A (en) * | 2019-03-27 | 2019-05-24 | 中国人民解放军陆军工程大学 | A kind of control synthetic method of different crystal forms manganese dioxide |
| CN112794304A (en) * | 2020-12-15 | 2021-05-14 | 杭州电子科技大学 | Method for preparing biochar through interface induction assembly |
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