CN106629717A - Preparation method of activated carbon electrode material used for ionic liquid electrolyte supercapacitor - Google Patents
Preparation method of activated carbon electrode material used for ionic liquid electrolyte supercapacitor Download PDFInfo
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- CN106629717A CN106629717A CN201611191925.4A CN201611191925A CN106629717A CN 106629717 A CN106629717 A CN 106629717A CN 201611191925 A CN201611191925 A CN 201611191925A CN 106629717 A CN106629717 A CN 106629717A
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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Abstract
The invention discloses a preparation method of an activated carbon electrode material used for an ionic liquid electrolyte supercapacitor. The preparation method comprises the following steps: crushing saw dust into 40 meshes to 80 meshes in a particle size range; mixing the saw dust with phosphoric acid solution at 80 to 150 DEG C according to an impregnation ratio of 1:(1 to 6) and impregnating for 8 to 12 hours; pouring the saw dust into a porcelain crucible and putting in a chamber electric furnace, heating up at 1 to 10 DEG C/min to 700 to 1000 DEG C, and performing heat preservation for 1 to 3 hours; cooling to room temperature, and then taking out a carbonized material, washing with hot deionized water, and filtering; performing acid washing, and filtering; washing with deionized water until pH is between 6.4 and 7.6; drying activated carbon in a drying oven of 110 to 150 DEG C for 12 to 24 hours; and grinding the activated carbon to be greater than 400 meshes. Renewable biomass resources are adopted, so that the preparation method disclosed by the invention is green and environment-friendly, and sustainable development is achieved; as a phosphoric acid chemical activation method is adopted, the preparation method is easy to industrialize, simple and easy, and low-cost, and the activated carbon electrode material has a pore structure easy to adjust and control; after the electrode material is assembled into the ionic liquid electrolyte supercapacitor for electrochemical testing, the ionic liquid electrolyte supercapacitor shows excellent electrochemical performance, and the specific capacitance of the ionic liquid electrolyte supercapacitor reaches up to 162 F/g.
Description
Technical field
The invention belongs to ionic liquid electrolyte ultracapacitor phosphatase activity carbon electrode material preparing technical field, specifically
It is related to a kind of preparation method of ionic liquid electrolyte active carbon electrode material for super capacitor, using biomass resource China fir
Bits prepare phosphorous activated carbon for novel energy-storing element --- electrode material for electric double layer capacitor by phosphoric acid high temperature carbonization.
Background technology
Electrochemical double layer capacitor, is a kind of novel energy-storing element, because it has high power also known as ultracapacitor
Density and longer cycle life (105-106Secondary charge-discharge circulation), using the teaching of the invention it is possible to provide high power density is discharged, and be can be widely applied to
The aspects such as traffic, home electronic products, medical electronics product, military electronic product.But it is compared with battery etc., its energy density
(electric energy that unit volume or quality are discharged) is relatively low, limits its application.Improving the main method of energy density is：Use
The electrolyte of current potential window width or the specific capacitance of raising electrode material.
The electrolyte that at present ultracapacitor is used：Water system, organic system and the class electrolyte of ionic liquid three.With water system and have
Machine system electrolyte phase ratio, have that electrochemical window width, stable chemical nature, heat endurance are good, volatility is low due to ionic liquid,
Nonflammable, good cycle particular advantages, therefore it is to solve double layer capacitor energy to develop ionic liquid super capacitor
One of relatively low main method of density.
At present the electrode active material of ultracapacitor is mainly porous carbon material, including charcoal-aero gel, CNT,
Mesoporous carbon material, Graphene and activated carbon etc..The pore structure of activated carbon is to affect it as electrode material for super capacitor
Main structural reason.In theory, it is more flourishing with the hole that electrolyte ion size matches in activated carbon, the ratio of corresponding hole
Surface area is higher, then the specific capacitance of activated carbon is bigger.The flourishing activated carbon of micropore is applied to water system electrolyte, due to ion
The ion size of liquid electrolyte is bigger than the composition ion size of potassium hydroxide or sulfuric acid, accordingly, as ionic liquid electrolysis
The pore structure of the active carbon electrode material of matter ultracapacitor is also different.
The industrial conventional chemical activating agent for preparing activated carbon is KOH or NaOH.Disclose in CN101525132A
One kind is with starch (oxidative crosslinked starch, corn cationic starch, graft copolymerization starch, soluble starch or tapioca) as former
Material, potassium hydroxide is the method that activator produces activated carbon for super capacitors, and specific surface area is 2249m2/ g, 30%
Test in KOH electrolyte aqueous solutions, specific capacitance is up to 221F/g.Disclose a kind of potassium hydroxide in CN102718213A to live
The technique that change method prepares cotton stalk activated carbon.Cotton stalk is raw material, and potassium hydroxide prepares activated carbon, activated carbon for activator
Yield reaches 16.8%, and BET specific surface area is 2312m2/g.Although the activated carbon specific surface area used by above patent is high, micro-
Hole and mesopore proportion ability of regulation and control are poor, and pore structure is based on micropore.The ion size of ionic liquid electrolyte is electrolysed compared with water system
The ion size of matter is big, need using the highly developed activated carbon of mesopore, therefore, conventional potassium hydroxide or NaOH conduct
Activated carbon prepared by activator has been not suitable as the absorbent charcoal material of ionic liquid electrolyte ultracapacitor.
It is at present conventional activated carbon industrialized preparing process that phosphoric acid activation method prepares activated carbon, it have it is simple,
It is cheap, and tool is easy to the remarkable advantage of regulation and control pore structure, but because its activation temperature is no more than 550 DEG C, cause system
Standby activated carbon presents the property of insulator, therefore, a kind of employing high temperature phosphoric acid activation string of invention is former
The method for expecting this cheap raw material, prepares the method that can apply to ionic liquid super capacitor activated carbon.
The content of the invention：
It is an object of the invention to provide a kind of preparation of ionic liquid electrolyte active carbon electrode material for super capacitor
Method, using high temperature phosphoric acid activation cheap raw material string, prepares the work that can apply to ionic liquid super capacitor
Property charcoal, pore structure is adjustable, improve activated carbon electrodes specific capacitance and energy density, can be with significantly high energy storage device-ion
The performance of liquid ultracapacitor.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is：
A kind of preparation method of ionic liquid electrolyte active carbon electrode material for super capacitor, comprises the following steps：
(1) wood chip is crushed to into the mesh of 40 mesh of particle size range -80；
(2) it is respectively 1 according to impregnating ratio:The impregnating ratio of 1-6 is by the wood chip and phosphoric acid solution of step (1) at 80-150 DEG C
Hybrid infusion 8-12h；
(3) wood chip in step (2) is poured in porcelain crucible and is placed in chamber type electric resistance furnace, be warming up to 1-10 DEG C/min
700-1000 DEG C, and it is incubated 1-3h；
(4) carbonized material taken out in step (3) is cooled to after room temperature, is washed, is filtered with the deionized water of heat；
(5) by the activated carbon pickling in step (4), filtration；
(6) the activated carbon deionized water in step (5) is washed till into pH in 6.4-7.6；
(7) activated carbon in step (6) is so dried into 12-24h in 110-150 DEG C of baking oven；
(8) activated carbon in step (7) is ground to into the mesh of ＞ 400.
Step 1) in, described wood chip includes broadleaf and the softwood chips such as China fir, masson pine, poplar.
Step 2) in, impregnating ratio is 1:3.
Step 2) in, the hybrid infusion 10h at 80 DEG C.
Step 3) in, temperature is 800-950 DEG C.
Step 3) in, temperature is 900 DEG C.
Step 5) in, wash to neutrality.
It is to be remained in carbonized material of going out that the carbonized material for obtaining first is washed, filtered by the present invention with the deionized water of heat
Phosphoric acid and phosphoric acid oxide；Further washed, filtered with 0.1mol/L hydrochloric acid be in order to remove activated carbon in contain
Alkali metal oxide and the impurity such as hydroxide, obtain the extremely low activated carbon of content of ashes；The deionized water of last reusable heat
Washing, filter be in order to remove activated carbon in acid cleaning process remain hydrochloric acid, obtain pure active carbon electrode material.
Beneficial effect：Compared with prior art, advantages of the present invention is as follows：
1) raw material that the present invention is adopted is the reproducible biomass resource of circulation, and environmental protection, development are sustainable.
2) present invention adopt activation method be phosphoric acid chemical activation method be easy to industrialization, it is simple, cheap and
Tool is easy to regulate and control the remarkable advantage of pore structure.
3) activation temperature of the invention adopts 800-950-DEG C, the flourishing activated carbon of class graphite microcrystalline structure is obtained, improve
The conductance of activated carbon.
4) present invention used by the equal mesh of ＞ 400 of active carbon electrode material particle size range, ionic liquid electrolyte be easier into
Enter in activated carbon hole, improve the effective rate of utilization of activated carbon.
5) present invention makes the hole of activated carbon adjustable by changing dipping and carbonization temperature, it is adaptable to which ionic liquid is electrolysed
Matter, is conducive to improving the energy density of activated carbon electrodes ultracapacitor.
Specific embodiment
With reference to specific embodiment, the present invention is described further.
Embodiment 1
A kind of preparation method of ionic liquid electrolyte ultracapacitor activated carbon, step is as follows：
1) cedar sawdust is crushed to into particle size range for the mesh of 40 mesh -80.
2) dry weight 10g cedar sawdust is weighed in 300mL beakers, take impregnating ratio for 1:1 (the quality of raw material and 100% phosphoric acid
Than) solution 50mL in beaker, be stirred for being well mixed with glass bar, obtain the mixture of cedar sawdust and phosphoric acid.
3) mixture is placed in 80 DEG C of water-bath, hybrid infusion 10h, is stirred once every 1h, obtain what is impregnated
Cedar sawdust.
4) cedar sawdust for having impregnated is poured in porcelain crucible and is placed in chamber type electric resistance furnace, with 5 DEG C of .min-1It is warming up to charing temperature
900 DEG C of degree, and it is incubated charing 2h.
5) carbonized material taken out after room temperature is cooled to, is washed, is filtered with the deionized water of heat, remove H3PO4, deactivated
The activated carbon of agent.
6) chlorohydric acid pickling 6h, the filtration by the activated carbon of deactivator with 0.1mol/L, removes alkali metal oxide and hydrogen
The impurity such as oxide, obtain the extremely low activated carbon of content of ashes.
7) the extremely low activated carbon deionized water of content of ashes is washed till into pH in 6.4-7.6, removes HCl, obtain pure
Activated carbon sample.
8) pure activated carbon is dried into 12-24h in 110-150 DEG C of baking oven.
9) dried activated carbon agate mortar is ground to into the mesh of ＞ 400, obtains active carbon electrode material AC1-900.
Embodiment 2
A kind of preparation method of ionic liquid electrolyte ultracapacitor activated carbon, step is as follows：1) cedar sawdust is crushed
It is the mesh of 40 mesh -80 to particle size range.
2) dry weight 10g cedar sawdust is weighed in 300mL beakers, take impregnating ratio for 1:2 (the quality of raw material and 100% phosphoric acid
Than) solution 50mL in beaker, be stirred for being well mixed with glass bar, obtain the mixture of cedar sawdust and phosphoric acid.
3) mixture is placed in 80 DEG C of water-bath, hybrid infusion 10h, is stirred once every 1h, obtain what is impregnated
Cedar sawdust.
4) cedar sawdust for having impregnated is poured in porcelain crucible and is placed in chamber type electric resistance furnace, with 5 DEG C of .min-1It is warming up to charing temperature
900 DEG C of degree, and it is incubated charing 2h.
5) carbonized material taken out after room temperature is cooled to, is washed, is filtered with the deionized water of heat, remove H3PO4, deactivated
The activated carbon of agent.
6) chlorohydric acid pickling 6h, the filtration by the activated carbon of deactivator with 0.1mol/L, removes alkali metal oxide and hydrogen
The impurity such as oxide, obtain the extremely low activated carbon of content of ashes.
7) the extremely low activated carbon deionized water of content of ashes is washed till into pH in 6.4-7.6, removes HCl, obtain pure
Activated carbon sample.
8) pure activated carbon is dried into 12-24h in 110-150 DEG C of baking oven.
9) dried activated carbon agate mortar is ground to into the mesh of ＞ 400, obtains active carbon electrode material AC2-900.
Embodiment 3
A kind of preparation method of ionic liquid electrolyte ultracapacitor activated carbon, step is as follows：1) cedar sawdust is crushed
It is the mesh of 40 mesh -80 to particle size range.
2) dry weight 10g cedar sawdust is weighed in 300mL beakers, take impregnating ratio for 1:3 (the quality of raw material and 100% phosphoric acid
Than) solution 50mL in beaker, be stirred for being well mixed with glass bar, obtain the mixture of cedar sawdust and phosphoric acid.
3) mixture is placed in 80 DEG C of water-bath, hybrid infusion 10h, is stirred once every 1h, obtain what is impregnated
Cedar sawdust.
4) cedar sawdust for having impregnated is poured in porcelain crucible and is placed in chamber type electric resistance furnace, with 5 DEG C of .min-1It is warming up to charing temperature
900 DEG C of degree, and it is incubated charing 2h.
5) carbonized material taken out after room temperature is cooled to, is washed, is filtered with the deionized water of heat, remove H3PO4, deactivated
The activated carbon of agent.
6) chlorohydric acid pickling 6h, the filtration by the activated carbon of deactivator with 0.1mol/L, removes alkali metal oxide and hydrogen
The impurity such as oxide, obtain the extremely low activated carbon of content of ashes.
7) the extremely low activated carbon deionized water of content of ashes is washed till into pH in 6.4-7.6, removes HCl, obtain pure
Activated carbon sample.
8) pure activated carbon is dried into 12-24h in 110-150 DEG C of baking oven.
9) dried activated carbon agate mortar is ground to into the mesh of ＞ 400, obtains active carbon electrode material AC3-900.
Embodiment 4
A kind of preparation method of ionic liquid electrolyte ultracapacitor activated carbon, step is as follows：1) cedar sawdust is crushed
It is the mesh of 40 mesh -80 to particle size range.
2) dry weight 10g cedar sawdust is weighed in 300mL beakers, take impregnating ratio for 1:4 (the quality of raw material and 100% phosphoric acid
Than) solution 50mL in beaker, be stirred for being well mixed with glass bar, obtain the mixture of cedar sawdust and phosphoric acid.
3) mixture is placed in 80 DEG C of water-bath, hybrid infusion 10h, is stirred once every 1h, obtain what is impregnated
Cedar sawdust.
4) cedar sawdust for having impregnated is poured in porcelain crucible and is placed in chamber type electric resistance furnace, with 5 DEG C of .min-1It is warming up to charing temperature
900 DEG C of degree, and it is incubated charing 2h.
5) carbonized material taken out after room temperature is cooled to, is washed, is filtered with the deionized water of heat, remove H3PO4, deactivated
The activated carbon of agent.
6) chlorohydric acid pickling 6h, the filtration by the activated carbon of deactivator with 0.1mol/L, removes alkali metal oxide and hydrogen
The impurity such as oxide, obtain the extremely low activated carbon of content of ashes.
7) the extremely low activated carbon deionized water of content of ashes is washed till into pH in 6.4-7.6, removes HCl, obtain pure
Activated carbon sample.
8) pure activated carbon is dried into 12-24h in 110-150 DEG C of baking oven.
9) dried activated carbon agate mortar is ground to into the mesh of ＞ 400, obtains active carbon electrode material AC4-900.
Embodiment 5
A kind of preparation method of ionic liquid electrolyte ultracapacitor activated carbon, step is as follows：1) cedar sawdust is crushed
It is the mesh of 40 mesh -80 to particle size range.
2) dry weight 10g cedar sawdust is weighed in 300mL beakers, take impregnating ratio for 1:3 (the quality of raw material and 100% phosphoric acid
Than) solution 50mL in beaker, be stirred for being well mixed with glass bar, obtain the mixture of cedar sawdust and phosphoric acid.
3) mixture is placed in 80 DEG C of water-bath, hybrid infusion 10h, is stirred once every 1h, obtain what is impregnated
Cedar sawdust.
4) cedar sawdust for having impregnated is poured in porcelain crucible and is placed in chamber type electric resistance furnace, with 5 DEG C of .min-1It is warming up to charing temperature
800 DEG C of degree, and it is incubated charing 2h.
5) carbonized material taken out after room temperature is cooled to, is washed, is filtered with the deionized water of heat, remove H3PO4, deactivated
The activated carbon of agent.
6) chlorohydric acid pickling 6h, the filtration by the activated carbon of deactivator with 0.1mol/L, removes alkali metal oxide and hydrogen
The impurity such as oxide, obtain the extremely low activated carbon of content of ashes.
7) the extremely low activated carbon deionized water of content of ashes is washed till into pH in 6.4-7.6, removes HCl, obtain pure
Activated carbon sample.
8) pure activated carbon is dried into 12-24h in 110-150 DEG C of baking oven.
9) dried activated carbon agate mortar is ground to into the mesh of ＞ 400, obtains active carbon electrode material AC3-800.
Embodiment 6
A kind of preparation method of ionic liquid electrolyte ultracapacitor activated carbon, step is as follows：1) cedar sawdust is crushed
It is the mesh of 40 mesh -80 to particle size range.
2) dry weight 10g cedar sawdust is weighed in 300mL beakers, take impregnating ratio for 1:3 (the quality of raw material and 100% phosphoric acid
Than) solution 50mL in beaker, be stirred for being well mixed with glass bar, obtain the mixture of cedar sawdust and phosphoric acid.
3) mixture is placed in 80 DEG C of water-bath, hybrid infusion 10h, is stirred once every 1h, obtain what is impregnated
Cedar sawdust.
4) cedar sawdust for having impregnated is poured in porcelain crucible and is placed in chamber type electric resistance furnace, with 5 DEG C of .min-1It is warming up to charing temperature
850 DEG C of degree, and it is incubated charing 2h.
5) carbonized material taken out after room temperature is cooled to, is washed, is filtered with the deionized water of heat, remove H3PO4, deactivated
The activated carbon of agent.
6) chlorohydric acid pickling 6h, the filtration by the activated carbon of deactivator with 0.1mol/L, removes alkali metal oxide and hydrogen
The impurity such as oxide, obtain the extremely low activated carbon of content of ashes.
7) the extremely low activated carbon deionized water of content of ashes is washed till into pH in 6.4-7.6, removes HCl, obtain pure
Activated carbon sample.
8) pure activated carbon is dried into 12-24h in 110-150 DEG C of baking oven.
9) dried activated carbon agate mortar is ground to into the mesh of ＞ 400, obtains active carbon electrode material AC3-850.
Embodiment 7
A kind of preparation method of ionic liquid electrolyte ultracapacitor activated carbon, step is as follows：1) cedar sawdust is crushed
It is the mesh of 40 mesh -80 to particle size range.
2) dry weight 10g cedar sawdust is weighed in 300mL beakers, take impregnating ratio for 1:3 (the quality of raw material and 100% phosphoric acid
Than) solution 50mL in beaker, be stirred for being well mixed with glass bar, obtain the mixture of cedar sawdust and phosphoric acid.
3) mixture is placed in 80 DEG C of water-bath, hybrid infusion 10h, is stirred once every 1h, obtain what is impregnated
Cedar sawdust.
4) cedar sawdust for having impregnated is poured in porcelain crucible and is placed in chamber type electric resistance furnace, with 5 DEG C of .min-1It is warming up to charing temperature
950 DEG C of degree, and it is incubated charing 2h.
5) carbonized material taken out after room temperature is cooled to, is washed, is filtered with the deionized water of heat, remove H3PO4, deactivated
The activated carbon of agent.
6) chlorohydric acid pickling 6h, the filtration by the activated carbon of deactivator with 0.1mol/L, removes alkali metal oxide and hydrogen
The impurity such as oxide, obtain the extremely low activated carbon of content of ashes.
7) the extremely low activated carbon deionized water of content of ashes is washed till into pH in 6.4-7.6, removes HCl, obtain pure
Activated carbon sample.
8) pure activated carbon is dried into 12-24h in 110-150 DEG C of baking oven.
9) dried activated carbon agate mortar is ground to into the mesh of ＞ 400, obtains active carbon electrode material AC3-950.
Embodiment 8
Active carbon electrode material obtained in embodiment 1-7 is carried out into specific surface area, pore structure, elementary analysis, resistivity
Test, and by prepared active carbon electrode material and polytetrafluoroethylene (PTFE) (binding agent), acetylene black (conductive agent) in mass ratio 8:
1:1 mixing, is subsequently adding 5-10 times of amount of the mixture of absolute ethyl alcohol, stirs into slurry and is well mixed, by the mud being well mixed
Slurry drying, with roll squeezer smooth (thickness is 0.6-0.7mm) is suppressed, and is made into the card punch of diameter 11mm big in nickel foam
Little identical disk.Kept for the 5-10 seconds nickel foam and electrode slice bond the two under 5-10MPa pressure with YP-2 tablet press machines
Together.And make ionic liquid electrolyte ultracapacitor and investigate its chemical property.Its physical and chemical performance parameter refers to table 1.
Constituent content, specific surface area, pore structure, the resistance parameter of the activated carbon of table 1
From table 1 it follows that Jing after chemical activation, prepared active carbon electrode material has high specific surface area,
Concentrate on 1300-1600m2.g-1Left and right；The hole of activated carbon is easily regulated and controled by changing impregnating ratio and carbonization temperature, to electrification
The maximum mesoporous accounting highest of performance contribution is learned, 66% is accounted for, thus AC3-900 shows in the capacitor excellent electrochemistry
Performance, its quality specific capacitance is maximum, up to 162F/g.
Claims (7)
1. a kind of preparation method of ionic liquid electrolyte active carbon electrode material for super capacitor, it is characterised in that include
Following steps：
（1）Wood chip is crushed to into the mesh of 40 mesh of particle size range -80；
（2）1 is respectively according to impregnating ratio:The impregnating ratio of 1-6 is by step（1）Wood chip and phosphoric acid solution at 80-150 DEG C mix
Close dipping 8-12h；
（3）By step（2）In cedar sawdust pour in porcelain crucible and be placed in chamber type electric resistance furnace, 700- is warming up to 1-10 DEG C/min
1000 DEG C, and it is incubated 1-3h；
（4）It is cooled to after room temperature and takes out step（3）In carbonized material, with heat deionized water wash, filter；
（5）By step（4）In activated carbon pickling, filter；
（6）By step（5）In activated carbon deionized water be washed till pH in 6.4-7.6；
（7）By step（6）In activated carbon 12-24h is so dried in 110-150 DEG C of baking oven；
（8）By step（7）In activated carbon be ground to the mesh of ＞ 400.
2. the preparation method of ionic liquid electrolyte active carbon electrode material for super capacitor according to claim 1,
It is characterized in that：Step 1）In, described wood chip is selected from broadleaf and softwood chips.
3. the preparation method of ionic liquid electrolyte active carbon electrode material for super capacitor according to claim 1,
It is characterized in that：Step 2）In, impregnating ratio is 1: 3.
4. the preparation side of the ionic liquid electrolyte active carbon electrode material for super capacitor according to claim 1 or 3
Method, it is characterised in that：Step 2）In, the hybrid infusion 10h at 80 DEG C.
5. the preparation method of ionic liquid electrolyte active carbon electrode material for super capacitor according to claim 1,
It is characterized in that：Step 3）In, temperature is 800-950 DEG C.
6. the preparation side of ionic liquid electrolyte active carbon electrode material for super capacitor according to claim 1 or 5
Method, it is characterised in that：Step 3）In, temperature is 900 DEG C.
7. the preparation method of ionic liquid electrolyte active carbon electrode material for super capacitor according to claim 1,
It is characterized in that：Step 5）In, wash to neutrality.
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| CN109835898A (en) * | 2019-04-12 | 2019-06-04 | 北京工商大学 | A kind of preparation method of the biomass porous carbon material of citric acid grain of adjustable micropore ratio |
| CN115677716A (en) * | 2022-09-09 | 2023-02-03 | 华北电力大学 | High-value utilization method of cotton processing waste |
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| CN103496700A (en) * | 2013-09-11 | 2014-01-08 | 华南理工大学 | Method for preparing active carbon from pyrolysis residues of cedarwood sawdust |
| CN104803383A (en) * | 2015-04-13 | 2015-07-29 | 中南大学 | Method for preparing activated carbon for supercapacitors from camphor tree leaves |
| CN105016337A (en) * | 2014-04-17 | 2015-11-04 | 中国科学院上海硅酸盐研究所 | Active carbon material used for supercapacitor electrodes and preparation method thereof |
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| CN103496700A (en) * | 2013-09-11 | 2014-01-08 | 华南理工大学 | Method for preparing active carbon from pyrolysis residues of cedarwood sawdust |
| CN105016337A (en) * | 2014-04-17 | 2015-11-04 | 中国科学院上海硅酸盐研究所 | Active carbon material used for supercapacitor electrodes and preparation method thereof |
| CN104803383A (en) * | 2015-04-13 | 2015-07-29 | 中南大学 | Method for preparing activated carbon for supercapacitors from camphor tree leaves |
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| CN109835898A (en) * | 2019-04-12 | 2019-06-04 | 北京工商大学 | A kind of preparation method of the biomass porous carbon material of citric acid grain of adjustable micropore ratio |
| CN115677716A (en) * | 2022-09-09 | 2023-02-03 | 华北电力大学 | High-value utilization method of cotton processing waste |
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