CN104425136A - Carbon-based electrode material, preparing method of carbon-based electrode material and super capacitor - Google Patents

Carbon-based electrode material, preparing method of carbon-based electrode material and super capacitor Download PDF

Info

Publication number
CN104425136A
CN104425136A CN201310400894.9A CN201310400894A CN104425136A CN 104425136 A CN104425136 A CN 104425136A CN 201310400894 A CN201310400894 A CN 201310400894A CN 104425136 A CN104425136 A CN 104425136A
Authority
CN
China
Prior art keywords
electrode material
base electrode
charcoal base
carbon
based electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201310400894.9A
Other languages
Chinese (zh)
Other versions
CN104425136B (en
Inventor
王宏宇
郑程
齐力
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN201310400894.9A priority Critical patent/CN104425136B/en
Publication of CN104425136A publication Critical patent/CN104425136A/en
Application granted granted Critical
Publication of CN104425136B publication Critical patent/CN104425136B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/42—Powders or particles, e.g. composition thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • 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

Abstract

The invention provides a carbon-based electrode material, a preparing method of the carbon-based electrode material and a super capacitor. Middle phase carbon micro balls are treated in inert atmosphere or reducing atmosphere at 0 DEG C to 600 DEG C, and the carbon-based electrode material can be obtained. Compared with the prior art, the carbon-based electrode material uses the middle phase carbon micro balls subjected to heating treatment as the electrode material, firstly, through the heating treatment, organic substances in the middle phase carbon micro balls can be removed, so that the structure of the obtained carbon-based electrode material is compact, and the vibration compaction density is increased; then, the specific surface area of the carbon-based electrode material is smaller, and correspondingly, the quantity of active functional groups on the surface of the carbon-based electrode material is small, so that the catalysis effect of the functional groups on the irreversible decomposition of electrolyte can be effectively inhabited, further, an interface of the electrode material and the electrolyte is stabilized, the invertible degree of charge (ion) storage is improved, and the work voltage and the specific capacitance of the super capacitor are effectively improved; next, the carbon-based electrode materials can be obtained through the heating treatment, the preparing method is simple, and the operation is easy.

Description

Charcoal base electrode material and preparation method thereof, ultracapacitor
Technical field
The invention belongs to capacitor technology field, particularly relate to charcoal base electrode material and preparation method thereof, ultracapacitor.
Background technology
In order to alleviate day by day serious energy crisis and environmental problem, countries in the world government all in the development carrying forward vigorously new-energy automobile industry, as electric automobile.But current the faced ultimate challenge of electric automobile is exactly apparatus for storing electrical energy, no matter be lead-acid battery, lithium battery, or fuel cell, the problem such as all have that cost is high, the life-span is short, continual mileage is short and the charging interval is long, therefore, the electrical storage device of people to electric automobile proposes the requirements such as low cost, high power capacity, long-life and high safety.
In recent years, a kind of novel, efficient, practical energy accumulating device-ultracapacitor receives much concern, and is expected to the main apparatus for storing electrical energy becoming New Generation of Electric Vehicle.Ultracapacitor is made up of positive pole, negative pole, electrolyte and the barrier film between both positive and negative polarity, become again capacitor with super capacity, electrochemical capacitor, double electric layer capacitor, gold electric capacity, storage capacitor or farad capacitor, be a kind of new energy energy storage device having traditional capacitor and these two kinds of energy storage device advantages of secondary cell concurrently grown up the seventies and eighties in 20th century, its capacity can reach hundreds of to thousands of farad.Compare with secondary cell with traditional capacitor, the energy force rate ordinary capacitor that ultracapacitor stores electric charge is high, and have that charge/discharge rates is fast, efficiency is high, environmentally safe, have extended cycle life, the scope of application is wide, fail safe high, the blank between traditional capacitor and secondary cell has been filled up in its appearance.In fact, ultracapacitor not only has huge potential using value on electric automobile, rushes current feedback circuit also will play a significant role in communication, space flight, national defence etc. as height, and therefore ultracapacitor has become the focus of people's research.
Electrode is the core component of ultracapacitor, is made up of active material and conducting matrix grain, and both positive and negative polarity active material is the source producing electric energy, is the important component part determining battery fundamental characteristics.Material with carbon element because it is cheap and easy to get, operating temperature range is wide, specific area is controlled, pore structure is flourishing, chemical stability is high, mature production technology, the advantage such as environmentally friendly be widely used in preparing electrode material.
The maximum charcoal base electrode material of present use comprises active carbon, activated carbon fiber, charcoal-aero gel, carbon nano-tube and template carbon, mainly through chemical vapour deposition technique, template and high temperature pyrolysis etc.But these methods or complex steps, process are complicated, or condition is harsh, limits its further application in ultracapacitor and large-scale promotion.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of charcoal base electrode material and preparation method thereof, ultracapacitor, and this charcoal base electrode material preparation method is simple.
The invention provides a kind of charcoal base electrode material, by MCMB in inert atmosphere or reducing atmosphere, process under 0 DEG C ~ 600 DEG C conditions and obtain.
Preferably, the specific area of described charcoal base electrode material is 0.01 ~ 10m 2/ g.
Present invention also offers a kind of preparation method of charcoal base electrode material, comprise the following steps:
By MCMB in inert atmosphere or reducing atmosphere, 0 DEG C ~ 600 DEG C process, obtain charcoal base electrode material.
Preferably, the temperature of described process is 60 DEG C ~ 600 DEG C.
Preferably, the temperature of described process is 300 DEG C ~ 500 DEG C.
Preferably, the time of described process is 2 ~ 12h.
Preferably, described inert atmosphere is selected from one or more in helium, argon gas and nitrogen.
Preferably, described reducing atmosphere is the mist of hydrogen and inert gas.
Preferably, the content of described hydrogen is 5% ~ 20% of mist volume.
Present invention also offers a kind of ultracapacitor, comprise positive pole, negative pole, electrolyte and barrier film, described positive pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described negative pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described electrolyte is the organic solution of quaternary ammonium salt; Described positive pole and negative pole have one at least for the charcoal base electrode material described in claim 1 ~ 2 or the charcoal base electrode material prepared by claim 3 ~ 9 any one.
The invention provides a kind of charcoal base electrode material and preparation method thereof, ultracapacitor, by MCMB in inert atmosphere or reducing atmosphere, 0 DEG C ~ 600 DEG C process, charcoal base electrode material can be obtained.Compared with prior art, the present invention is using the MCMB through heat treated as electrode material, and first, heat treated can remove the organic species in MCMB, and the charcoal base electrode material structure obtained is compacted, and tap density increases; Secondly, the specific area of this charcoal base electrode material is less, accordingly, the amount of the active function groups on its surface is little, thus the catalytic action of these functional groups to the irreversible decomposition of electrolyte can be effectively suppressed, and then stabilize this electrode material and electrolyte interface, improve the degree of reversibility that electric charge (ion) stores, therefore this charcoal base electrode material effectively can improve operating voltage and the ratio capacitance of ultracapacitor; Again, this charcoal base electrode material can obtain through heat treated, and preparation method is simple to operation.
Experimental result shows, the ratio capacitance of the ultracapacitor adopting charcoal base electrode material of the present invention to prepare can reach 60mAh/g.
Accompanying drawing explanation
The stereoscan photograph of the charcoal base electrode material that Fig. 1 is MCMB, the embodiment of the present invention 1 ~ 5 prepares;
Fig. 2 is the N of MCMB 2adsorption-desorption isothermal linearity curve figure;
Fig. 3 is the N of the charcoal base electrode material that the embodiment of the present invention 1 prepares 2adsorption-desorption isothermal linearity curve figure;
Fig. 4 is the N of the charcoal base electrode material that the embodiment of the present invention 2 prepares 2adsorption-desorption isothermal linearity curve figure;
Fig. 5 is the N of the charcoal base electrode material that the embodiment of the present invention 3 prepares 2adsorption-desorption isothermal linearity curve figure;
Fig. 6 is the N of the charcoal base electrode material that the embodiment of the present invention 4 prepares 2adsorption-desorption isothermal linearity curve figure;
Fig. 7 is the N of the charcoal base electrode material that the embodiment of the present invention 5 prepares 2adsorption-desorption isothermal linearity curve figure;
Fig. 8 is the specific capacity curve chart of the button cell that the embodiment of the present invention 6 ~ 9 prepares;
Fig. 9 is the specific capacity curve chart of the button cell that the embodiment of the present invention 10 ~ 16 prepares;
Figure 10 is the specific capacity curve chart of the button cell that the embodiment of the present invention 17 ~ 18 prepares;
Figure 11 is the cycle life curve chart of the button cell that the embodiment of the present invention 18 prepares;
Figure 12 is the specific capacity curve chart of the button cell that the embodiment of the present invention 19 ~ 22 prepares;
Figure 13 is the specific capacity curve chart of the button cell that the embodiment of the present invention 23 ~ 24 prepares;
Figure 14 is the cycle life curve chart of the button cell prepared in the embodiment of the present invention 25;
Figure 15 is the specific capacity curve chart of the button cell prepared in the embodiment of the present invention 26;
Figure 16 is the cycle life curve chart of the button cell prepared in the embodiment of the present invention 27.
Embodiment
The invention provides a kind of preparation method of charcoal base electrode material, MCMB is processed in inert atmosphere or reducing atmosphere, under 0 DEG C ~ 600 DEG C conditions, obtains charcoal base electrode material.
Wherein, described MCMB is MCMB well known to those skilled in the art, there is no special restriction, and its source is for commercially available; Described inert atmosphere is inert gas well known to those skilled in the art, there is no special restriction, and the present invention is preferably selected from one or more in helium, argon gas and nitrogen, is more preferably helium, argon gas or nitrogen; Described reducing atmosphere is preferably the mist of hydrogen and inert gas, and wherein the content of hydrogen is preferably 5% ~ 20% of mist volume, is more preferably 8% ~ 15%.
MCMB processed in inert atmosphere or reducing atmosphere, the temperature of described process is preferably 60 DEG C ~ 600 DEG C, is more preferably 300 DEG C ~ 500 DEG C; The time of described process is preferably 0 ~ 12h, is more preferably 2 ~ 10h, is more preferably 4 ~ 10h.
According to the present invention, MCMB preferably naturally cools to normal temperature after heat treated in inert atmosphere or reducing atmosphere, obtains charcoal base electrode material.
MCMB is heat treated in inert gas, can remove low boiling organic species wherein, and the charcoal base electrode material structure obtained comparatively is compacted, and tap density increases; And this charcoal base electrode material can obtain through heat treated, and preparation method is simple to operation.
Present invention also offers a kind of charcoal base electrode material prepared by said method, by MCMB in inert atmosphere or reducing atmosphere, process under 0 DEG C ~ 600 DEG C conditions and obtain.
The condition of described inert atmosphere, reducing atmosphere and process is all same as above, does not repeat them here.
According to the present invention, the specific area of described charcoal base electrode material is less than or equal to 10m 2/ g, is preferably 0.01 ~ 10m 2/ g, is more preferably 0.1 ~ 10m 2/ g, then be preferably 0.1 ~ 5m 2/ g.
Present invention also offers a kind of ultracapacitor, comprise positive pole, negative pole, electrolyte and barrier film, described positive pole is selected from the one in charcoal base electrode material, graphite and active carbon; Described negative pole is selected from the one in charcoal base electrode material, graphite and active carbon; Described electrolyte is the organic solution of quaternary ammonium salt; Described positive pole and negative pole have one at least for charcoal base electrode material, are the charcoal base electrode material of above-mentioned preparation when preferably positive pole is different from negative pole, can only have one for charcoal base electrode material.
The present invention is with the organic solution of quaternary ammonium salt for electrolyte, and it is containing metal or metal ion not, under high voltages, can not form metal deposition, and then can not block the hole of electrode material inside, thus extend the cycle life of ultracapacitor on electrolysis material surface.Described quaternary ammonium salt is preferably selected from tetrafluoro boric acid tetramethyl-ammonium (TMABF 4), trifluoromethanesulfonic acid tetramethyl-ammonium (TMACF 3sO 3), perchloric acid tetramethyl-ammonium (TMAClO 4), tetraethylammonium tetrafluoroborate (TEABF 4), tetraethylammonium hexafluorophosphate (TEAPF 6), tetraethylammonium perchlorate (TEAClO 4), tetrapropyl ammonium tetrafluoroborate (TPABF 4), tetrapropyl ammonium perchlorate (TPAClO 4), tetrafluoro boric acid 4-butyl amine (TBABF 4), tetrabutylammonium perchlorate (TBAClO 4), triethyl methyl ammonium tetrafluoroborate (TEMABF 4), perchloric acid triethyl methyl ammonium (TEMAClO 4), tetrafluoro boric acid dimethyl diethyl ammonium (DEDMABF 4), perchloric acid dimethyl diethyl ammonium (DEDMAClO 4), tetrafluoro boric acid trimethylethyl ammonium (ETMABF 4), perchloric acid trimethylethyl ammonium (ETMAClO 4), tetrafluoro boric acid spiro quaternary ammonium salt (SBP (BF 4) 2) and perchloric acid spiro quaternary ammonium salt (SBP (ClO 4) 2) in one or more.
The organic solvent of the organic solution of described quaternary ammonium salt is preferably one or more in propene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate and GBL, is more preferably wherein one or both.
According to the present invention, the concentration of the organic solution of quaternary ammonium salt is preferably 1 ~ 1.5mol/L; Described barrier film is barrier film well known to those skilled in the art, there is no special restriction, is preferably glass fibre, is more preferably double glazing fiber in the present invention.
The electrode material that the present invention is ultracapacitor with charcoal base electrode material, the specific area of this charcoal base electrode material is less, accordingly, the amount of the active function groups on its surface is little, thus the catalytic action of these functional groups to the irreversible decomposition of electrolyte can be effectively suppressed, and then stabilize this electrode material and electrolyte interface, improve the degree of reversibility that electric charge (ion) stores, therefore this charcoal base electrode material effectively can improve operating voltage and the ratio capacitance of ultracapacitor.
In order to further illustrate the present invention, below in conjunction with embodiment, a kind of charcoal base electrode material provided by the invention and preparation method thereof, ultracapacitor are described in detail.
Reagent used in following examples is commercially available.
Embodiment 1
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen protection, 400 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze MCMB, obtain its stereoscan photograph, as shown in a in Fig. 1.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 1, obtain its stereoscan photograph, as shown in b in Fig. 1.Can find out by Fig. 1, the charcoal base electrode material that the present invention obtains has spherical structure, close structure, surface irregularity.
Utilize full-automatic specific area and multi-well assay instrument to analyze MCMB, obtain its N 2adsorption-desorption isothermal linearity curve, as shown in Figure 2, in figure ● curve is N 2adsorption isotherm linearity curve, in figure ▲ curve is N 2desorption isothermal curve.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 1, obtain its N 2adsorption-desorption isothermal linearity curve, as shown in Figure 3, in figure ● curve is N 2adsorption isotherm linearity curve, in figure ▲ curve is N 2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 1 according to the curve calculation of Fig. 3 is 0.095m 2/ g.
Embodiment 2
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen protection, 500 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 2, obtain its stereoscan photograph, as shown in c in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 2, obtain its N 2adsorption-desorption isothermal linearity curve, as shown in Figure 4, in figure ● curve is N 2adsorption isotherm linearity curve, in figure ▲ curve is N 2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 2 according to the curve calculation of Fig. 4 is 0.9486m 2/ g.
Embodiment 3
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen protection, 600 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 3, obtain its stereoscan photograph, as shown in d in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 3, obtain its N 2adsorption-desorption isothermal linearity curve, as shown in Figure 5, in figure ● curve is N 2adsorption isotherm linearity curve, in figure ▲ curve is N 2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 3 according to the curve calculation of Fig. 5 is 0.0926m 2/ g.
Embodiment 4
MCMB is loaded porcelain boat, puts into tube furnace, under argon shield, 500 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 4, obtain its stereoscan photograph, as shown in e in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 4, obtain its N 2adsorption-desorption isothermal linearity curve, as shown in Figure 6, in figure ● curve is N 2adsorption isotherm linearity curve, in figure ▲ curve is N 2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 4 according to the curve calculation of Fig. 6 is 0.0233m 2/ g.
Embodiment 5
MCMB is loaded porcelain boat, puts into tube furnace, under nitrogen and hydrogen gas mixture (content of hydrogen is 10% of mist volume) are protected, 500 DEG C of heat treated 6h, are cooled to normal temperature, obtain charcoal base electrode material.
Utilize scanning electron microscopy to analyze the charcoal base electrode material obtained in embodiment 5, obtain its stereoscan photograph, as shown in f in Fig. 1.
Utilize full-automatic specific area and multi-well assay instrument to analyze the charcoal base electrode material obtained in embodiment 5, obtain its N 2adsorption-desorption isothermal linearity curve, as shown in Figure 7, in figure ● curve is N 2adsorption isotherm linearity curve, in figure ▲ curve is N 2desorption isothermal curve.The specific area obtaining the charcoal base electrode material obtained in embodiment 2 according to the curve calculation of Fig. 7 is 0.7212m 2/ g.
Embodiment 6
10mg MCMB and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 6 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 8 ● shown in curve.
Embodiment 7
The charcoal base electrode material obtained in 10mg embodiment 1 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 7 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in △ curve in Fig. 8.
Embodiment 8
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 8 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 8 shown in curve, in Fig. 9 shown in curve.
Embodiment 9
The charcoal base electrode material obtained in 10mg embodiment 3 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 9 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in zero curve in Fig. 8.
As shown in Figure 8, with the charcoal base electrode material obtained in the charcoal base electrode material obtained in MCMB, embodiment 1 and embodiment 2 for negative pole, graphite is positive pole, and quaternary ammonium salt organic solution is that the specific capacity of the ultracapacitor of electrolyte can reach nearly 50mAh/g; The specific capacity of the ultracapacitor being negative pole with the charcoal base electrode material obtained in embodiment 3 is about 30mAh/g.
Embodiment 10
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 0.1mol/L TMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 10 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9 shown in curve.
Embodiment 11
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LTEABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 11 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9 ● shown in curve.
Embodiment 12
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 0.8mol/L TPABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 12 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9 ▲ curve shown in.
Embodiment 13
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LTBABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 13 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in zero curve in Fig. 9.
Embodiment 14
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LTEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 14 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in curve in Fig. 9.
Embodiment 15
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LDEDMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 15 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Fig. 9 shown in curve.
Embodiment 16
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1mol/LETMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 16 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in △ curve in Fig. 9.
Embodiment 17
The charcoal base electrode material obtained in 10mg embodiment 4 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 17 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 10 ▲ curve shown in.
Embodiment 18
The charcoal base electrode material obtained in 10mg embodiment 5 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take graphite as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 18 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as shown in zero curve in Figure 10.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 18 to test, discharge and recharge 600 times under 0 ~ 4V operating voltage and 1mA current density, obtains its cycle life curve, as shown in figure 11, wherein a is discharge capacity, and b is coulombic efficiency.As shown in Figure 11, the capability retention of the button cell that embodiment 18 obtains in 600 charge and discharge process is higher, illustrates that its cycle life is better.
Embodiment 19
10mg MCMB and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 19 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 12 ▲ curve shown in.
Embodiment 20
The charcoal base electrode material obtained in 10mg embodiment 1 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 20 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 12 shown in curve.
Embodiment 21
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 21 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtain its specific capacity curve chart, with shown in zero curve in Figure 13 as shown in zero curve in Figure 12.
Embodiment 22
The charcoal base electrode material obtained in 10mg embodiment 3 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 22 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 12 ● shown in curve.
Embodiment 23
The charcoal base electrode material obtained in 10mg embodiment 4 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 23 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 13 ▲ curve shown in.
Embodiment 24
The charcoal base electrode material obtained in 10mg embodiment 5 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1.5mol/L TEMABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 24 to test, discharge and recharge under 0 ~ 4V operating voltage and 1mA current density, obtains its specific capacity curve chart, as in Figure 13 shown in curve.
As shown in Figure 13, to obtain charcoal base electrode material for negative pole in embodiment 2, embodiment 4 and embodiment 5, active carbon is positive pole, and quaternary ammonium salt organic solution is that the specific capacity of the ultracapacitor of electrolyte can reach 60mAh/g.
Embodiment 25
The charcoal base electrode material obtained in 10mg embodiment 5 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains negative pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as positive pole, layer glass fiber is barrier film, 1mol/L TEABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 25 to test, discharge and recharge 600 times under 0 ~ 4V operating voltage and 1mA current density, obtains its cycle life curve chart, as shown in figure 14, wherein a is discharge capacity, and b is coulombic efficiency.From in Figure 14, the capability retention of the button cell obtained in embodiment 25 in 600 charge and discharge process is very high, illustrates that its cycle life is good.
Embodiment 26
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains positive pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as negative pole, layer glass fiber is barrier film, 1mol/L TEABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 26 to test, discharge and recharge under 0 ~ 3.5V operating voltage and 1mA current density, obtain its specific capacity curve chart, as shown in figure 15, as shown in Figure 15, the specific capacity of the ultracapacitor that the charcoal base electrode material prepared in embodiment 2 obtains as positive pole can reach 30mAh/g.
Embodiment 27
The charcoal base electrode material obtained in 10mg embodiment 2 and 5mg electroconductive binder are mixed and be coated in collector aluminium on the net, compressing tablet film forming, after 120 DEG C of vacuumize 12h, obtains positive pole, proceeds in the saturated glove box of anhydrous and oxygen-free argon gas for subsequent use.Take active carbon as negative pole, layer glass fiber is barrier film, 1mol/L TEABF 4organic solution be that electrolyte is assembled into button cell.
Connect the chemical property of LAND series battery test macro to the button cell obtained in embodiment 27 to test, discharge and recharge 1000 times under 0 ~ 3.5V operating voltage and 1mA current density, obtains its cycle life curve chart, as shown in figure 16, wherein a is discharge capacity, and b is coulombic efficiency.As shown in Figure 16, the capability retention of ultracapacitor in 1000 charge and discharge process that the charcoal base electrode material prepared in embodiment 2 obtains as positive pole is very high, illustrates that its cycle life is better.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (10)

1. a charcoal base electrode material, is characterized in that, by MCMB in inert atmosphere or reducing atmosphere, process under 0 DEG C ~ 600 DEG C conditions and obtain.
2. charcoal base electrode material according to claim 1, is characterized in that, the specific area of described charcoal base electrode material is 0.01 ~ 10m 2/ g.
3. a preparation method for charcoal base electrode material, is characterized in that, comprises the following steps:
By MCMB in inert atmosphere or reducing atmosphere, 0 DEG C ~ 600 DEG C process, obtain charcoal base electrode material.
4. preparation method according to claim 3, is characterized in that, the temperature of described process is 60 DEG C ~ 600 DEG C.
5. preparation method according to claim 3, is characterized in that, the temperature of described process is 300 DEG C ~ 500 DEG C.
6. preparation method according to claim 3, is characterized in that, the time of described process is 2 ~ 12h.
7. preparation method according to claim 3, is characterized in that, described inert atmosphere is selected from one or more in helium, argon gas and nitrogen.
8. preparation method according to claim 3, is characterized in that, described reducing atmosphere is the mist of hydrogen and inert gas.
9. preparation method according to claim 8, is characterized in that, the content of described hydrogen is 5% ~ 20% of mist volume.
10. a ultracapacitor, comprise positive pole, negative pole, electrolyte and barrier film, it is characterized in that, described positive pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described negative pole is selected from the one in the charcoal base electrode material described in claim 1 ~ 2 or charcoal base electrode material, graphite and the active carbon prepared by claim 3 ~ 9 any one; Described electrolyte is the organic solution of quaternary ammonium salt; Described positive pole and negative pole have one at least for the charcoal base electrode material described in claim 1 ~ 2 or the charcoal base electrode material prepared by claim 3 ~ 9 any one.
CN201310400894.9A 2013-09-05 2013-09-05 Charcoal base electrode material and preparation method thereof, ultracapacitor Active CN104425136B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310400894.9A CN104425136B (en) 2013-09-05 2013-09-05 Charcoal base electrode material and preparation method thereof, ultracapacitor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310400894.9A CN104425136B (en) 2013-09-05 2013-09-05 Charcoal base electrode material and preparation method thereof, ultracapacitor

Publications (2)

Publication Number Publication Date
CN104425136A true CN104425136A (en) 2015-03-18
CN104425136B CN104425136B (en) 2018-08-28

Family

ID=52973857

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310400894.9A Active CN104425136B (en) 2013-09-05 2013-09-05 Charcoal base electrode material and preparation method thereof, ultracapacitor

Country Status (1)

Country Link
CN (1) CN104425136B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1985340A (en) * 2004-07-09 2007-06-20 大阪瓦斯株式会社 Active carbon for electric double layer capacitor, active carbon electrode for electric double layer capacitor, and electric double layer capacitor therewith
CN101079510A (en) * 2007-06-25 2007-11-28 中南大学 A super capacitance cell
CN101916856A (en) * 2010-08-05 2010-12-15 深圳市贝特瑞新能源材料股份有限公司 Cathode material for lithium-ion power and energy storage battery and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1985340A (en) * 2004-07-09 2007-06-20 大阪瓦斯株式会社 Active carbon for electric double layer capacitor, active carbon electrode for electric double layer capacitor, and electric double layer capacitor therewith
CN101079510A (en) * 2007-06-25 2007-11-28 中南大学 A super capacitance cell
CN101916856A (en) * 2010-08-05 2010-12-15 深圳市贝特瑞新能源材料股份有限公司 Cathode material for lithium-ion power and energy storage battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHENG ZHENG ET AL.: "Non-porous activated mesophase carbon microbeads as a negative electrode material for asymmetric electrochemical capacitors", 《JOURNAL OF POWER SOURCES》 *

Also Published As

Publication number Publication date
CN104425136B (en) 2018-08-28

Similar Documents

Publication Publication Date Title
Wang et al. A novel zinc-ion hybrid supercapacitor for long-life and low-cost energy storage applications
Chen et al. Preparation of activated carbon from cotton stalk and its application in supercapacitor
CN103730644B (en) Silicon-silicon oxide-carbon composite negative pole material of lithium ion battery preparation method
CN104779376B (en) A kind of lithium sulfur battery anode material, preparation method and lithium-sulfur cell
CN101385183B (en) Electrochemical energy storage device
US9613759B2 (en) Method for preparing fluorine/nitrogen co-doped graphitized carbon microspheres with high volumetric specific capacitance
CN103346293A (en) Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery
CN107611411B (en) Preparation method and application of three-dimensional hierarchical porous nitrogen-doped carbon-coated silicon composite material
CN103700859A (en) Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material
CN108922790B (en) Preparation method and application of composite material
CN103072986A (en) Method for preparing cotton stalk based active carbon electrode material by adopting gradient constant-temperature activation method
CN109686589B (en) Preparation method of lithium ion supercapacitor electrode material BCN nanotube
CN103050293A (en) Hard-carbon-based chemical power supply with long service life
CN106876687A (en) A kind of preparation method of carbon coating silicon quantum dot composite lithium ion battery cathode material
CN104098078B (en) Activation MCMB, its preparation method and ultracapacitor
CN101740233B (en) Vermicular mesoporous carbon/Bi2O3 composite electrode material as well as preparation method and application thereof
CN104916456A (en) High-energy-density super capacitor and preparation method thereof
CN111834130A (en) Collapsed carbon-based nano cage electrode material and preparation method thereof
CN108365210A (en) A kind of activated carbon carbon-sulfur materials and its preparation method and application
CN105355872A (en) Preparation method for carbon-based lithium ion battery electrode material
CN103390746A (en) Method for improving performance of lithium ion battery cathode material lithium titanate
Wei et al. P-Doped Cotton Stalk Carbon for High-Performance Lithium-Ion Batteries and Lithium–Sulfur Batteries
CN105098239A (en) Graphene lithium ion battery electrolyte
CN104401991A (en) Method for preparing activated carbon with high specific surface area by using conyza canadensis
CN105576239A (en) Preparation process and application of Cu3P/C-Cu negative electrode material without binding agent

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant