CN105016337B - A kind of absorbent charcoal material and preparation method thereof can be used for electrode of super capacitor - Google Patents
A kind of absorbent charcoal material and preparation method thereof can be used for electrode of super capacitor Download PDFInfo
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- CN105016337B CN105016337B CN201410153937.2A CN201410153937A CN105016337B CN 105016337 B CN105016337 B CN 105016337B CN 201410153937 A CN201410153937 A CN 201410153937A CN 105016337 B CN105016337 B CN 105016337B
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Abstract
The present invention relates to a kind of absorbent charcoal materials and preparation method thereof can be used for electrode of super capacitor, the absorbent charcoal material handles petroleum coke powder by the composite activating agent containing alkali and phosphorus compound and obtains, the absorbent charcoal material is phosphorous composite activated carbon, and phosphorus atoms content is 1000ppm~20000ppm in the absorbent charcoal material.
Description
Technical field
The present invention relates to a kind of absorbent charcoal materials and preparation method thereof, and in particular to one kind can be used for electrode of super capacitor
Absorbent charcoal material and preparation method thereof.
Background technology
Double layer capacitor (Electric Double Layer Capacitor, EDLC) is also referred to as ultracapacitor, is profit
The electric double layer formed between carbon materials and electrolyte interface with activated carbon etc. stores the novel accumulation of energy original paper of charge.It has electricity
The intermediate characteristic of induction type capacitor and secondary cell.
The storing up electricity mechanism of double layer capacitor is lived by formation electric double layer storage charge between electrode material and electrolyte
Property electrode material of the Carbon Materials as ultracapacitor, performance depends primarily on internal pore structure, including pore-size distribution, hole
Shape and hole appearance etc., it is to obtain the key point of high performance active carbon to efficiently control pore structure.As supercapacitor applications are led
The continuous expansion in domain, to the structure and performance of required activated carbon, the hole in being especially distributed to activated carbon pore size within the scope of 2-5nm
More stringent requirements are proposed for appearance.In order to improve the Kong Rong in activated carbon pore size distribution within the scope of 2-5nm, people have developed catalysis and have lived
Change method, polymer blend technique method, template charring and organic gel method etc., but all there is a problem of that specific surface area is relatively low, no
The ultracapacitor that performance is stable, specific capacitance is high can be obtained.
Activated carbon prepared by alkali (KOH, NaOH or LiOH) activation method developed in recent years has large specific surface area, electricity
The features such as capacity is high.CN101844765B discloses a kind of method for preparation of active carbon for carbon electrode of super capacitor, by coal
Asphaltic base, intermediate phase pitch-based, petroleum coke base and needle coke base amphipathic Carbon Materials among one kind, press matter with potassium hydroxide
Measure ratio 1：2~4 are mixed and added into deionized water, stir, and drying, grinding obtains mixed-powder, then to mixed-powder lazy
Property gas shield under carry out 700~900 DEG C at activate, product after cooling, cleaning, drying, grind up to ultracapacitor use
Activated carbon.Activated carbon for super capacitors described in CN101525132 is obtained through carbonizing, activating using starch as raw material；But it carbonizes
Material and the weight proportion of potassium hydroxide solid are up to 1：4~8.The usage amount of preparation method KOH disclosed in these patents is larger,
Production cost is high, is unsuitable for industrialized production, and its pore-size distribution concentrates in 2nm range of micropores below, affects electricity
Diffusion of the liquid ion on electrode material is solved, is unfavorable for forming electric double layer, the electrode material as ultracapacitor cannot obtain
The Fabrication of High Specific Capacitance expected.Further, since the usage amount of alkali is 3~8 times of carbonaceous raw material, the waste of alkali, Er Qiexu are not only caused
A large amount of alkaline waste water is handled, the requirement to production is also very harsh.
CN101837975A discloses a kind of microwave complex activation method preparing ultracapacitor porous charcoal, with carbon containing object
Mixture is raw material, adds the composite activating agent and catalyst of KOH and NaOH, is added to reactant using microwave irradiation
Heat, generates physical-chemical reaction and with microburst effect, and then promotes the formation of porous carbon structure, then washed and dried
Super porous carbon is finally made in journey.CN101964259A is disclosed prepares electrode material for super capacitor with high sulfur petroleum coke
Method after high sulfur petroleum coke is crushed and screened, is dried under the conditions of 100 DEG C, then by the high-sulfur oil after KOH, NaOH and drying
Burnt particle activates at 650 DEG C~850 DEG C, and the high sulfur petroleum coke base carbon material of activation is made；Again the high sulfur petroleum coke of activation
Base carbon material is down to room temperature, is filtered after washed to neutral, vacuum drying, obtains capacitor electrode material.It is above-mentioned both adopt
It is activated with KOH and NaOH composite activating agents, although reducing the dosage of alkali, can effectively improve specific capacity, production cost is still
It is so very high, and the recycling of later stage alkali and the sewage disposal of removal process can cause large effect to environment.
CN101356607B and CN102856081A is all made of phosphoric acid and is activated to activated carbon and phosphorus compound has been made
Composite activated carbon, obtained product remove deash at high temperature under high pressure, retain phosphorus complex chemical compound appropriate, phosphorus atoms
Content is 1000~3000ppm, but thus obtained phosphorus compound combined active carbon is mostly micropore (average fine pore 1.7nm-
It 2.1nm) is distributed, is unfavorable for forming electric double layer, to relatively low as electrode material for super capacitor specific capacity.
The limitation for how overcoming the above method obtains a kind of high performance activated carbon, has become the research in the field
One of hot spot.
Invention content
The present invention is directed to overcome defect existing for above-mentioned method for preparation of active carbon, the present invention provides one kind can be used for it is super
Absorbent charcoal material of electrode for capacitors and preparation method thereof.
The present invention provides a kind of absorbent charcoal materials can be used for electrode of super capacitor, and the absorbent charcoal material is by containing
The composite activating agent of alkali and phosphorus compound processing petroleum coke powder obtains, and the absorbent charcoal material is phosphorous composite activated carbon, institute
It is 1000ppm~20000ppm to state phosphorus atoms content in absorbent charcoal material.
Preferably, the specific surface area of the absorbent charcoal material is 1600m2/ g~2500m2/ g, of the absorbent charcoal material
The duct occupation rate that aperture is 2nm~5nm in grain is 20%~50%.
The present invention also provides a kind of method preparing material described in claims 1 or 2, the method includes：
1) it is dissolved in distilled water, stirs evenly, as multiplicity reactivation after mixing alkali by certain mass ratio with phosphorus compound
Agent solution uses；
2) using petroleum coke powder and polar organic solvent as raw material, compound activator solution made from step 1) is added in the two
In, it is placed after stirring evenly, obtains mixture；
3) mixture obtained in step 2) is stirred evenly, after to be dried, is activated in vacuum or protective atmosphere,
Room temperature is cooled to after activation；
4) by the powder pickling that activation obtains in step 3), then neutrality is washed to distillation and is drying to obtain the activated carbon
Material.
Preferably, the mass ratio of alkali and phosphorus compound is 1 in the step 1):The dosage of (0.1~5), distilled water is alkali
With 0.5~10 times of phosphorus compound gross mass.
Preferably, the alkali is NaOH and/or KOH, the phosphorus compound is sodium phosphate, potassium phosphate, dibastic sodium phosphate, phosphoric acid
At least one of hydrogen potassium.
Preferably, being placed 0.1~10 hour after stirring evenly in the step 1), it is cooled to room temperature.
Preferably, the addition of step 2) the petrochina coke powder can be 0.1~1 times of alkali and phosphorus compound gross mass.
Preferably, the granularity of step 2) the petrochina coke powder can be 1~100 micron.
Preferably, in the step 2) addition of polar organic solvent can be 1 gram of petroleum coke powder be added 0.05mL~
0.5mL polar organic solvents.
Preferably, polar organic solvent can be at least one of methanol, ethyl alcohol, acetone in the step 2).
Preferably, can be placed after being stirred evenly in the step 2) 0.1~10 hour.
Preferably, mixture can stir 0.1~10 hour at 30~100 DEG C in the step 3), then 50~300
It is thermally dried at DEG C.
Preferably, activation carries out in activation furnace in the step 3), the heating rate of activation furnace can be 1 DEG C/min~
20 DEG C/min, 500 DEG C~1200 DEG C are warming up to, heat preservation activation 0.5~10 hour.
Preferably, protective atmosphere can be at least one of argon gas, nitrogen in the step 3), other inertia can also be used
Gas is as protection gas.
Preferably, in the step 4) can by the powder chlorohydric acid pickling after the activation, a concentration of the 0.5 of the hydrochloric acid
~10mol/L.
Beneficial effects of the present invention：
(1) for the present invention using the mixture of alkali and phosphorus compound as composite activating agent, activator level is few, cost compared with
It is low, the shortcomings of activator corrosivity is strong, usage amount is big, pollution environment is overcome in prior art；
(2) tap density of activated carbon and the hole occupation rate of mesoporous can be improved by improving alkali ratio in composite activating agent, be improved
Phosphorus compound ratio can improve the specific capacitance and durability of activated carbon in composite activating agent；
(3) phosphorous composite activated carbon degree of graphitization prepared by is higher, particle diameter distribution uniformly, the hole occupation rate of mesoporous
High, large specific surface area.
Specific implementation mode
It is further illustrated the present invention below in conjunction with following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The invention discloses a kind of preparation methods of electrode of super capacitor absorbent charcoal material.For super capacitor electrode
The requirement of pole material comparison surface area and electric conductivity, the present invention is intended to provide a kind of high-specific surface area of pore structure based on mesoporous
Absorbent charcoal material is to improve the specific capacitance and durability of ultracapacitor.The absorbent charcoal material is using petroleum coke powder as carbon
Source reduces petroleum coke and activates difficulty by using a kind of structure of phosphorous composite activating agent processing adjustment petroleum coke graphite microcrystal,
Prepare a kind of phosphorous composite activated carbon of ultracapacitor.The chemical activating agent dosage that preparation method of the present invention uses
Few, product composite activated carbon pore structure easy-regulating, yield are high, of low cost, are used for electrode material for super capacitor, specific capacitance
Greatly, excellent in te pins of durability.Present invention combination alkali activates and two methods of phosphorus compound combined active carbon, it is proposed that a kind of alkali and phosphatization
Close the preparation method of object composite activating agent activation modification activated carbon, preparation process is simple, cost few using activator level compared with
It is low, environmentally protective.The present invention is intended to provide a kind of high-specific surface area, mesoporous for can be used for electrode material for super capacitor of preparing
The method of the high phosphorous composite activated carbon of hole occupation rate, to improve the specific volume of ultracapacitor.
Electrode material for super capacitor of the present invention is phosphorous composite activated carbon, and phosphorus atoms content is
1000ppm~20000ppm, BET specific surface area 1600m2/ g~2500m2/ g, aperture is that the duct of 2nm~5nm accounts in particle
It is 20%~50% to have rate.
Electrode of super capacitor of the present invention is prepared with activated carbon to be included the following steps：
(1) it is dissolved in distilled water after mixing alkali by certain mass ratio with phosphorus compound, stirs evenly, be cooled to room temperature work
It is used for compound activator solution；
(2) compound activator solution is added in raw material petroleum coke powder and polar organic solvent, is placed after stirring evenly,
Obtain mixture；
(3) mixture is stirred 0.1~10 hour under conditions of temperature is 30~100 DEG C, is heated in an atmosphere
It is dry, it is subsequently placed in activation furnace, is activated in protective atmosphere, furnace cooling is to room temperature after activation；
(4) by the powder chlorohydric acid pickling after the activation, then neutrality is washed to distillation, 60~100 DEG C in air
It is dry.
One of technology of preparing of the present invention is to be pre-configured with compound activator solution, by alkali in the step (1)
It is dissolved in distilled water after being mixed by certain mass ratio with phosphorus compound, alkali presses 1 with phosphorus compound:The mass ratio of (0.1~5) is mixed
It closes, the dosage of distilled water is 0.5~10 times of alkali and phosphorus compound gross mass.
The alkali and phosphorus compound of the configuration compound activator solution, alkali can be NaOH, KOH etc., and phosphorus compound can
To be sodium phosphate, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate etc..
It is dissolved in distilled water after mixing sodium hydroxide with sodium phosphate in the step (1), 0.1~10 is placed after stirring evenly
Hour.
The addition of the petroleum coke powder is 0.1~1 times of alkali and phosphorus compound gross mass.Specifically, the step
(2) addition of petrochina coke powder can be 0.1~1 times of sodium hydroxide and sodium phosphate gross mass.
The granularity of the petroleum coke powder is 1~100 micron.
The addition of polar organic solvent, which is 1 gram of petroleum coke powder addition 0.05mL~0.5mL polarity, in the step (2) has
Solvent.
The polar organic solvent is methanol, ethyl alcohol or acetone etc..
Compound activator solution is added in petroleum coke powder and polar organic solvent in the step (2), is put after stirring evenly
Set to 0 .1~10 hour.
Mixture described in the step (3) stirs 0.1~10 hour under conditions of temperature is 30~100 DEG C, Yu great
It is thermally dried for 50~300 DEG C in gas.
One of technology of preparing of the present invention is activation process, is subsequently placed in activation furnace in the step (3),
It is activated in protective atmosphere, the heating rate of activation furnace is 1 DEG C/min~20 DEG C/min, and the treatment temperature of the activation is
500 DEG C~1200 DEG C, the soaking time of the activation is 0.5h~10h.
The protective atmosphere can be the inert gas shieldings gas such as vacuum either argon gas, nitrogen or argon hydrogen gaseous mixture
Atmosphere.
By the powder chlorohydric acid pickling after the activation, a concentration of 0.5~10mol/ of the hydrochloric acid in the step (4)
L。
Electrode of super capacitor activated carbon of the present invention and preparation method thereof is compared with existing prepare, feature
It is：(1) present invention is using the mixture of alkali and phosphorus compound as composite activating agent, and activator level is few, and cost is relatively low, gram
The shortcomings of activator corrosivity is strong, usage amount is big, pollution environment has been taken in prior art；
(2) tap density of activated carbon and the hole occupation rate of mesoporous can be improved by improving alkali ratio in composite activating agent, be improved
Phosphorus compound ratio can improve the specific capacitance and durability of activated carbon in composite activating agent；
(3) phosphorous composite activated carbon degree of graphitization prepared by is higher, particle diameter distribution uniformly, the hole occupation rate of mesoporous
High, large specific surface area.
It is further illustrated the present invention below in conjunction with following embodiments, it should be appreciated that following embodiment is served only for the present invention
It is further described, should not be understood as limiting the scope of the invention, those skilled in the art is according to the present invention
Some nonessential modifications and adaptations that the above is made all belong to the scope of protection of the present invention.Following examples are specifically warm
Degree, time etc. are also only an examples in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary concrete numerical value.
Embodiment 1
It is dissolved in 30mL distilled water, stirs evenly after 12g sodium hydroxides are mixed with 7.2g sodium phosphates, be cooled to room temperature,
6g petroleum coke powders and 1.2mL ethyl alcohol (chemistry is pure) are added thereto, 60min is placed after stirring evenly, obtains mixture.It will mixing
Material stirs 1h under conditions of 60 DEG C, is thermally dried for 150 DEG C, is subsequently placed in activation furnace, in nitrogen protection in air
Under with the heating rate of 5 DEG C/min furnace temperature is risen to 700 DEG C, cool to room temperature with the furnace after heat preservation activation 1h, then use concentration
Then the chlorohydric acid pickling of 5mol/L is washed to neutrality with distillation, it is to dry 10h in 100 DEG C of vacuum drying chambers to be placed in temperature, is obtained
Phosphorous composite activated carbon.The composite activated carbon that 0.8g is phosphorous is taken, by phosphorous composite activated carbon, conductive black, polytetrafluoroethyl-ne
Alkene is 85 in mass ratio:10:5 uniformly mixing, slurry is coated on nickel foam collector, is prepared into the pressure of 20MP super
Capacitor electrode slice, 1mol/LNa2SO4Aqueous solution is electrolyte, and polypropylene film is diaphragm, is assembled into button capacitor.By institute
Obtained super button capacitor is in 70 DEG C of thermostat with HJ-201 type charge-discharge tests device (Big Dipper electrician society manufactures)
Electric performance test is carried out, after applying 1.6V voltages to super button capacitor first, with 10mA/cm2Constant current density electricity
Electricity is banished, the specific capacitance at initial stage is found out according to the discharge curve of gained.Then 1.6V voltages are applied to super button capacitor
After continuing 500 hours, still with 10mA/cm2Constant current density current discharge, durability is found out according to the discharge curve of gained
Specific capacitance after experiment compares change rate (%) of the specific capacitance after durability experiment relative to the specific capacitance at initial stage.It surveys
Examination data are shown in Table 1.
Embodiment 2
It is dissolved in 20mL distilled water, stirs evenly after 8g sodium hydroxides are mixed with 2.4g sodium phosphates, be cooled to room temperature
To compound activator solutions, 2g petroleum coke powders and 0.5mL ethyl alcohol (chemistry is pure) are added thereto, 60min is placed after stirring evenly,
Obtain mixture.Mixture is stirred into 2h under conditions of temperature is 70 DEG C, is thermally dried for 150 DEG C in air, then
It is placed in activation furnace, furnace temperature is risen to 800 DEG C with the heating rate of 10 DEG C/min under nitrogen protection, keep the temperature after activating 1h with stove
It is cooled to room temperature, then pickling, washing, drying process obtains phosphorous composite activated carbon with example 1.Electrode preparation method
And battery assembling, test condition are the same as example 1.Test data is shown in Table 1.
Embodiment 3
It is dissolved in 30mL distilled water, stirs evenly after 12g sodium hydroxides are mixed with 3.6g sodium phosphates, be cooled to room temperature
To compound activator solutions, 4g petroleum coke powders and 0.8mL ethyl alcohol (chemistry is pure) are added thereto, 60min is placed after stirring evenly,
Obtain mixture.Mixture is stirred into 3h under conditions of temperature is 50 DEG C, is thermally dried for 150 DEG C in air, then
It is placed in activation furnace, furnace temperature is risen to 800 DEG C with the heating rate of 10 DEG C/min under nitrogen protection, keep the temperature after activating 2h with stove
It is cooled to room temperature, then pickling, washing, drying process obtains phosphorous composite activated carbon with example 1.Electrode preparation method
And battery assembling, test condition are the same as example 1.Test data is shown in Table 1.
Embodiment 4
It is dissolved in 40mL distilled water, stirs evenly after 15g sodium hydroxides are mixed with 4.8g sodium phosphates, be cooled to room temperature
To compound activator solutions, 3g petroleum coke powders and 0.6mL ethyl alcohol (chemistry is pure) are added thereto, 60min is placed after stirring evenly,
Obtain mixture.Mixture is stirred into 3h under conditions of temperature is 60 DEG C, is thermally dried for 150 DEG C in air, then
It is placed in activation furnace, furnace temperature is risen to 900 DEG C with the heating rate of 10 DEG C/min under nitrogen protection, keep the temperature after activating 1h with stove
It is cooled to room temperature, then pickling, washing, drying process obtains phosphorous composite activated carbon with example 1.Electrode preparation method
And battery assembling, test condition are the same as example 1.Test data is shown in Table 1.
Table is in 1 as can be seen that phosphorous composite activated carbon 1000ppm~20000ppm, BET specific surface area are
1500m2/ g~2500m2/ g, the duct occupation rate that aperture is 2nm~5nm in particle is 20%~50%.After durability experiment
Specific capacitance relative to the specific capacitance at initial stage change rate substantially all near 90%, illustrate to answer using of the present invention phosphorous
The ultracapacitor for closing active carbon electrode material has good durability.
Table 1
The present invention is using the mixture of alkali and phosphorus compound as composite activating agent, and activator level is few, and cost is relatively low, gram
The shortcomings of activator corrosivity is strong, usage amount is big, pollution environment has been taken in prior art；Prepared phosphorous composite activated carbon
Degree of graphitization is higher, particle diameter distribution is uniform, the hole occupation rate of mesoporous is high, large specific surface area.
Claims (13)
1. a kind of absorbent charcoal material can be used for electrode of super capacitor, which is characterized in that the absorbent charcoal material is by containing alkali
Petroleum coke powder is activated at 500 DEG C~1200 DEG C in vacuum or protective atmosphere with the composite activating agent of phosphorus compound and is obtained
It arrives, the mass ratio of alkali and phosphorus compound is 1:（0.3~0.6）, the alkali is NaOH and/or KOH, and the phosphorus compound is phosphoric acid
At least one of sodium, potassium phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, the absorbent charcoal material is phosphorous composite activated carbon, described
Phosphorus atoms content is 1000ppm~20000ppm in absorbent charcoal material, and the specific surface area of the absorbent charcoal material is 1600m2/g
~2500m2/ g, the duct occupation rate that aperture is 2nm~5nm in the particle of the absorbent charcoal material is 20%~50%.
2. a kind of method preparing material described in claim 1, which is characterized in that the method includes：
1）Alkali and phosphorus compound are pressed 1:（0.3~0.6）It is dissolved in distilled water, stirs evenly, as compound after mass ratio mixing
Activator solution uses, and the alkali is NaOH and/or KOH；
2）Using petroleum coke powder and polar organic solvent as raw material, step 1 is added in the two）In compound activator solution obtained,
It is placed after stirring evenly, obtains mixture；
3）By step 2）In obtained mixture stir evenly, after to be dried, 500 DEG C~1200 in vacuum or protective atmosphere
It DEG C is activated, room temperature is cooled to after activation；
4）By step 3）It is middle to activate obtained powder pickling, then neutrality is washed to distillation be drying to obtain the active raw material of wood-charcoal
Material.
3. according to the method described in claim 2, it is characterized in that, the step 1）The dosage of middle distilled water is that alkali is closed with phosphatization
0.5~10 times of object gross mass.
4. according to the method described in claim 2, it is characterized in that, placing 0.1~10 after stirring evenly in the step 1)
Hour, it is cooled to room temperature.
5. according to the method described in claim 2, it is characterized in that, the step 2）The addition of petrochina coke powder is alkali and phosphorus
0.1~1 times of compound gross mass.
6. according to the method described in claim 2, it is characterized in that, the step 2）The granularity of petrochina coke powder is 1~100 micro-
Rice.
7. according to the method described in claim 2, it is characterized in that, the step 2）The addition of middle polar organic solvent is 1
0.05mL~0.5mL polar organic solvents are added in gram petroleum coke powder.
8. according to the method described in claim 2, it is characterized in that, the step 2）Middle polar organic solvent be methanol, ethyl alcohol,
At least one of acetone.
9. according to the method described in claim 2, it is characterized in that, the step 2）In stir evenly after place it is 0.1~10 small
When.
10. according to the method described in claim 2, it is characterized in that, the step 3）Middle mixture stirs at 30~100 DEG C
It 0.1~10 hour, is then thermally dried at 50~300 DEG C.
11. according to the method described in claim 2, it is characterized in that, the step 3）Middle activation carries out in activation furnace, activation
The heating rate of stove is 1 DEG C/min~20 DEG C/min, is warming up to 500 DEG C~1200 DEG C, heat preservation activation 0.5~10 hour.
12. according to the method described in claim 2, it is characterized in that, the step 3）Middle protective atmosphere is in argon gas, nitrogen
It is at least one.
13. according to any method in claim 2-12, which is characterized in that the step 4）It is middle will be after the activation
Powder chlorohydric acid pickling, a concentration of 0.5~10mol/L of the hydrochloric acid.
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| CN106629717A (en) * | 2016-12-21 | 2017-05-10 | 南京林业大学 | Preparation method of activated carbon electrode material used for ionic liquid electrolyte supercapacitor |
| CN110745824A (en) * | 2019-11-21 | 2020-02-04 | 哈尔滨工业大学 | Method for regulating and controlling coal-based porous carbon pore matching based on trace potassium source catalytic activation |
| CN111115627A (en) * | 2019-12-26 | 2020-05-08 | 河北工业职业技术学院 | Treatment method of tar residues |
| CN112661149A (en) * | 2020-12-24 | 2021-04-16 | 四川金汇能新材料股份有限公司 | Preparation method of graphite negative electrode material, negative electrode material and lithium ion battery |
| CN115321513B (en) * | 2022-08-29 | 2024-01-19 | 安徽工业大学 | Preparation and application of asphalt-based phosphorus-doped porous carbon material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101702379A (en) * | 2009-11-20 | 2010-05-05 | 青岛生物能源与过程研究所 | Method for preparing non-symmetrical electrochemical supercapacitor and electrode materials |
| CN102856081A (en) * | 2012-08-29 | 2013-01-02 | 福建省鑫森炭业股份有限公司 | Phosphorus compound composite active carbon as well as preparation method and application thereof |
| US20130211158A1 (en) * | 2006-11-08 | 2013-08-15 | The Curators Of The University Of Missouri | High surface area carbon and process for its production |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130211158A1 (en) * | 2006-11-08 | 2013-08-15 | The Curators Of The University Of Missouri | High surface area carbon and process for its production |
| CN101702379A (en) * | 2009-11-20 | 2010-05-05 | 青岛生物能源与过程研究所 | Method for preparing non-symmetrical electrochemical supercapacitor and electrode materials |
| CN102856081A (en) * | 2012-08-29 | 2013-01-02 | 福建省鑫森炭业股份有限公司 | Phosphorus compound composite active carbon as well as preparation method and application thereof |
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