CN101525132A - Active carbon for super capacitor and a preparation method thereof - Google Patents
Active carbon for super capacitor and a preparation method thereof Download PDFInfo
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- CN101525132A CN101525132A CN200910113996A CN200910113996A CN101525132A CN 101525132 A CN101525132 A CN 101525132A CN 200910113996 A CN200910113996 A CN 200910113996A CN 200910113996 A CN200910113996 A CN 200910113996A CN 101525132 A CN101525132 A CN 101525132A
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- 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
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- 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 relates to an electrode material for an electrochemical super capacitor, more particularly to an active carbon for the super capacitor and a preparation method thereof. The inventive active carbon for the super capacitor is obtained by the steps of drying, carbonizing and activating starch that is taken as raw material. The preparation method thereof comprises the following steps of: 1) drying moisture in the starch; 2) putting the dried starch in an electric resistance furnace to be heated up to 350-550 DEG C under the protection of an inert gas, keeping constant temperature for 1-4 hours, and taking out after cooling to obtain a carbonizing material; 3) grinding and mixing the carbonizing material with potassium hydroxide saturated solution uniformly, drying the moisture and putting the mixture in the electric resistance furnace to be heated up to 750-850 DEG C under the protection of the inert gas, keeping constant temperature for 1-4 hours, and taking out the mixture after cooling to be ground, washing to a neutral state and drying to obtain the active carbon; the proportion by weight of the carbonizing material to potassium hydroxide solid is 1:4-8. The invention has extensive source of the raw materials, high specific surface area of the prepared active carbon and low production cost.
Description
Technical field:
The present invention relates to the electric chemical super capacitor electrode materials, be specially a kind of activated carbon for super capacitors; The invention still further relates to this preparation method of active carbon.
Background technology:
Ultracapacitor also claims electrochemical capacitor, is big 20～200 times novel energy storage device of the conventional condenser capacity of a kind of ratio.It is good that it has the pulse charge-discharge performance, and storage power big (specific energy is greater than 2.5Whkg-1), power big (specific power is greater than 500Wkg-1), light weight, have extended cycle life (above 100,000 times), use temperature wide (40 ℃～60 ℃) and charging be excellent specific properties such as (less than 3min) rapidly.And ultracapacitor need not safeguard throughout one's life, and it is environmentally friendly, pollution-free to use the back, thereby the green energy resource that is otherwise known as.Good characteristic based on ultracapacitor, people are widely used as the power supply of power truck with it, the instantaneous large-current power supply that the start-up system of oil engine and other heavy-duty car engine is required, the solar cell accessory power supply, aerospace equipment electricity consumption source, standby power supply is as temporary lighting, heating, electronic drawing water and the standby power supply of computer or the like, market outlook are wide, especially containing huge market potential in the environmental-protecting type electric automobile industry.
The research and development of electrode for super capacitor material at present mainly concentrate on carbon material, just like gac, vitreous carbon, fiber, gel, high-density graphite, pyrolytic polymer matrix and foam, carbon nanotube, high reactivity MCMB that obtains and cellular diamond with nanoaperture, rare metal oxide and conductive polymers etc.In the above-mentioned electrode materials, the raw materials for production of gac mainly contain plant class and mineral substance two parts.Wherein, the plant class is used as preparing the main raw material of gac to adopt trees or wood chip, and is well-known, though timber is renewable resources, because the arboreal growth cycle is long and be subjected to the restriction of the environmental protection and the eubiosis, and can not be a large amount of as the gac raw materials.In recent years, timber and wood chip shortage of resources are on the rise, and therefore, also have been subjected to restriction significantly with its Activated Carbon Production as raw material.Another kind of mineral substance raw material along with development of modern industry also will be developed totally, has been subjected to restriction greatly equally as the Activated Carbon Production of raw material.Therefore, constantly seek and produce the new raw material resources of gac, explore novel process, increase new variety, enlarge the Application of Brand Active Carbon field and remain one of task of activated carbon in China development.
In recent years, the disclosed new raw material that is used to prepare activated carbon for super capacitors of State Intellectual Property Office had: bamboo (publication number: CN101125650A), hard fruit shell (publication number: CN1824604A), straw (publication number: CN101037200A), resin (publication number: CN1291587A) etc.But up to now, do not see that having with starch is the report of feedstock production electrode material for super capacitor both at home and abroad.
Summary of the invention:
It is the activated carbon for super capacitors and preparation method thereof of feedstock production with starch that the technical problem to be solved in the present invention provides a kind of.Activated carbon for super capacitors specific surface area height provided by the invention, production cost is low.
Activated carbon for super capacitors of the present invention, it is to be raw material with starch, oven dry moisture after charing, activation step make; Wherein, described starch is oxidative crosslinked starch, corn cationic starch, graft copolymerization starch, Zulkovsky starch or tapioca (flour).
Described charing step is: get the starch of oven dry behind the moisture and place resistance furnace, be warming up to 350～550 ℃ under protection of inert gas, constant temperature 1～4h.
Described activation step is: the carbonized material grinding is mixed with the potassium hydroxide saturated solution, and oven dry moisture is placed in the resistance furnace, is warming up to 750～850 ℃ under protection of inert gas, constant temperature 1～4h; Wherein, described carbonized material and potassium hydroxide solid weight proportion are 1: 4～8.
The preparation method of activated carbon for super capacitors provided by the invention, its step is as follows:
1) starch is dried moisture; Described starch is oxidative crosslinked starch, corn cationic starch, graft copolymerization starch, Zulkovsky starch or tapioca (flour);
2) get the starch of oven dry behind the moisture and place resistance furnace, under protection of inert gas, be warming up to 350～550 ℃, constant temperature 1～4h, take out the cooling back, obtains carbonized material;
3) the carbonized material grinding is mixed with the potassium hydroxide saturated solution, oven dry moisture is placed in the resistance furnace, is warming up to 750～850 ℃ under protection of inert gas, constant temperature 1～4h, and the taking-up of cooling back grinds, and it is washed till neutrality, oven dry, promptly; Described carbonized material and potassium hydroxide solid weight proportion are 1: 4～8.
In the aforesaid method, step 2) and the temperature rise rate in the step 3) be 1～5 ℃.
Compared with prior art, the advantage of activated carbon for super capacitors of the present invention is:
1, is raw material with starch, has that raw material sources are wide, numerous in variety, low price, regeneration be with short production cycle, advantages such as environmentally safe;
2, the gac specific surface area height that makes, production cost is low; The ultracapacitor that adopts gac provided by the invention to do the electrode materials assembling has characteristics such as high-energy-density, product performance height;
3, the preparation method is simple, and is easy to operate.
Description of drawings:
The SEM figure of the activated carbon for super capacitors that Fig. 1: embodiment 1 makes;
Fig. 2: the activated carbon for super capacitors that embodiment 1 is made presents figure as the charging and discharging curve that electrode materials is assembled into the simulation ultracapacitor;
Fig. 3: the activated carbon for super capacitors that embodiment 1 is made is assembled into the simulation ultracapacitor as electrode materials, the cyclic voltammetry curve figure under different scanning rates (A:5mV/s, B:10mV/s, C:20mV/s, D:50mV/s);
Fig. 4: be assembled into the cyclic voltammetry curve figure (A:5mV/s, B:10mV/s, C:20mV/s, D:50mV/s) of simulation ultracapacitor under different scanning rates as electrode materials with commercially available gac.
Embodiment:
Activated carbon for super capacitors of the present invention, it is to be raw material with starch, oven dry moisture after charing, activation step make; Wherein, described starch is oxidative crosslinked starch, corn cationic starch, graft copolymerization starch, Zulkovsky starch or tapioca (flour).Described charing step is: get the starch of oven dry behind the moisture and place resistance furnace, be warming up to 350～550 ℃ under protection of inert gas, constant temperature 1～4h.Described activation step is: the carbonized material grinding is mixed with the potassium hydroxide saturated solution, and oven dry moisture is placed in the resistance furnace, is warming up to 750～850 ℃ under protection of inert gas, constant temperature 1～4h; Wherein.Described carbonized material and potassium hydroxide solid weight proportion are 1: 4～8.
The preparation method of activated carbon for super capacitors provided by the invention, its step is as follows:
1) starch is dried moisture; Described starch is oxidative crosslinked starch, corn cationic starch, graft copolymerization starch, Zulkovsky starch or tapioca (flour);
2) get the starch of oven dry behind the moisture and place resistance furnace, under protection of inert gas, be warming up to 350～550 ℃, constant temperature 1～4h, take out the cooling back, obtains carbonized material;
3) the carbonized material grinding is mixed with the potassium hydroxide saturated solution, oven dry moisture is placed in the resistance furnace, is warming up to 750～850 ℃ under protection of inert gas, constant temperature 1～4h, and the taking-up of cooling back grinds, and it is washed till neutrality, oven dry, promptly; Described carbonized material and potassium hydroxide solid weight proportion are 1: 4～8.
The temperature of starch when oven dry is difficult for too high, and to avoid the change of its structure and proterties, comparatively suitable to dry by the fire 12～24h in 100～120 ℃ of baking ovens, the drying condition described in the step 3) is identical therewith; Rare gas element is generally selected argon gas or nitrogen for use; The grinding granularity of the activation products that carbonized material and postorder obtain can be determined as required, is generally 100～200 orders; When the washing activation products, preferably use 60～80 ℃ hot wash, in washing, stir, make it comparatively fast reach neutral.
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to these embodiment.
Embodiment 1:
Take by weighing the 10g oxidative crosslinked starch; dry by the fire 12h in 120 ℃ of baking ovens, be contained in and insert tube type resistance furnace in the stainless steel vessel, controlling temperature rise rate with temperature controller then under the protection of Ar rare gas element is that 1 ℃/min is warmed up to 350 ℃; constant temperature 4h makes the starch charing become starch Jiao.Mix with the KOH saturated solution after the starch coke powder of gained is broken to 150 orders (starch Jiao: KOH solid=1: 4, weight ratio, as follows); Behind the baking 24h, place tube type resistance furnace in 120 ℃ baking oven, controlling temperature rise rate with temperature controller then under the protection of Ar rare gas element is that 1 ℃/min is warmed up to 850 ℃, and constant temperature 1.5h naturally cools to room temperature then.Taking-up grinds to 150 orders with mortar, add an amount of hot water, under magnetic agitation, stir 12h, and then be neutral with hot water repetitive scrubbing to pH value, dry by the fire 12h down at 120 ℃, promptly obtain activated carbon for super capacitors of the present invention, its SEM schemes as shown in Figure 1, and this gac actual measurement specific surface area is 2281.4m
2/ g.
Be assembled into the simulation ultracapacitor with the above-mentioned starch gac that makes as electrode materials, in 30% KOH aqueous electrolyte liquid, carry out electrochemical property test.In current density is 0.5A/g, charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, shows high characteristic ratio capacity, and the recycle ratio capacity is 217.6F/g first, charging and discharging curve presents typical triangular symmetry and distributes, as shown in Figure 2; Cyclic voltammetry curve under different scanning rates is the comparatively rectangle of rule, as shown in Figure 3.
Comparative Examples 1
With commercially available gac is that electrode materials is assembled into the simulation ultracapacitor, carries out electrochemical property test in 30% KOH aqueous electrolyte liquid.In current density is 0.5A/g, charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, the recycle ratio capacity is 156.7F/g first, cyclic voltammetry curve is the comparatively rectangle of rule under the low scanning speed of 5mV/s, along with scanning speed improves figure the distortion variation having taken place, has presented irregular rectangle.Fig. 4 is the cyclic voltammetry curve figure under its different scanning rates.
Embodiment 2:
Used starch is 10g corn cationic starch, and charing and activation condition are with embodiment 1.Gained gac actual measurement specific surface area is 1876.2m
2/ g.
The starch gac of gained is assembled into the simulation ultracapacitor as electrode materials, in 30% KOH aqueous electrolyte liquid, carries out electrochemical property test.In current density is 0.5A/g, and charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, and the recycle ratio capacity is 184.3F/g first, and charging and discharging curve presents typical triangular symmetry and distributes, and cyclic voltammetry curve is the comparatively rectangle of rule.
Embodiment 3:
Used starch is the 10g tapioca (flour), and charing and activation condition are with embodiment 1.Gained gac actual measurement specific surface area is 1939.8m
2/ g.
The starch gac of gained is assembled into the simulation ultracapacitor as electrode materials, in 30% KOH aqueous electrolyte liquid, carries out electrochemical property test.In current density is 0.5A/g, and charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, and the recycle ratio capacity is 197.4F/g first, and charging and discharging curve presents typical triangular symmetry and distributes, and cyclic voltammetry curve is the comparatively rectangle of rule.
Embodiment 4:
Used starch is the 10g Zulkovsky starch, and charing and activation condition are with embodiment 1.Gained gac actual measurement specific surface area is 2064.6m
2/ g.The starch gac of gained is assembled in the simulation ultracapacitor as electrode materials, in 30% KOH aqueous electrolyte liquid, carries out electrochemical property test.In current density is 0.5A/g, and charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, and the recycle ratio capacity is 209.2F/g first, and charging and discharging curve presents typical triangular symmetry and distributes, and cyclic voltammetry curve is the comparatively rectangle of rule.
Embodiment 5:
Used starch is 10g graft copolymerization starch, and charing and activation condition are with embodiment 1.Gained gac actual measurement specific surface area is 2117.1m
2/ g.
The starch gac of gained is assembled into the simulation ultracapacitor as electrode materials, in 30% KOH aqueous electrolyte liquid, carries out electrochemical property test.In current density is 0.5A/g, and charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, and the recycle ratio capacity is 201.4F/g first, and charging and discharging curve presents typical triangular symmetry and distributes, and cyclic voltammetry curve is the comparatively rectangle of rule.
Embodiment 6:
Take by weighing the 10g tapioca (flour); behind the baking 20h, be contained in and insert tube type resistance furnace in the stainless steel vessel in 120 ℃ of baking ovens, controlling temperature rise rate with temperature controller then under the protection of Ar rare gas element is that 5 ℃/min is warmed up to 500 ℃; constant temperature 1h makes the starch charing become starch Jiao.Mix (starch Jiao: KOH solid=1: 5) with the KOH saturated solution after the starch coke powder of gained is broken to 200 orders; Behind the baking 20h, place tube type resistance furnace in 120 ℃ baking oven, controlling temperature rise rate with temperature controller then under the protection of Ar rare gas element is that 2 ℃/min is warmed up to 750 ℃, and constant temperature 3h naturally cools to room temperature then.Taking-up grinds to 200 orders with mortar, adds an amount of hot water, stirs 10h under magnetic agitation, and then be neutral with hot water repetitive scrubbing to pH value, dry by the fire 12h down at 120 ℃, promptly obtain activated carbon for super capacitors of the present invention, this gac actual measurement specific surface area is 2212.7m
2/ g.
The starch gac of gained is assembled into the simulation ultracapacitor as electrode materials, in 30% KOH aqueous electrolyte liquid, carries out electrochemical property test.In current density is 0.5A/g, and charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, and the recycle ratio capacity is 201.3F/g first.
Embodiment 7
Take by weighing 10g corn cationic starch; behind the baking 24h, be contained in and insert tube type resistance furnace in the stainless steel vessel in 120 ℃ of baking ovens, controlling temperature rise rate with temperature controller then under the protection of Ar rare gas element is that 3 ℃/min is warmed up to 400 ℃; constant temperature 2h makes the starch charing become starch Jiao.Mix (starch Jiao: KOH solid=1: 8) with the KOH saturated solution after the starch coke powder of gained is broken to 100 orders; Behind the baking 12h, place tube type resistance furnace in 120 ℃ baking oven, controlling temperature rise rate with temperature controller then under the protection of Ar rare gas element is that 2 ℃/min is warmed up to 800 ℃, and constant temperature 2h naturally cools to room temperature then.Taking-up grinds to 100 orders with mortar, is neutral with hot water repetitive scrubbing to pH value, dries by the fire 12h down at 120 ℃, promptly obtains activated carbon for super capacitors of the present invention, and this gac actual measurement specific surface area is 2249.4m
2/ g.
The starch gac of gained is assembled into the simulation ultracapacitor as electrode materials, in 30% KOH aqueous electrolyte liquid, carries out electrochemical property test.In current density is 0.5A/g, and charging/discharging voltage is to carry out electrochemical property test under 0.00～1.20V condition, and the recycle ratio capacity is 221.3F/g first.
Claims (5)
1, a kind of activated carbon for super capacitors is characterized in that: it is to be raw material with starch, oven dry moisture after charing, activation step make; Wherein, described starch is oxidative crosslinked starch, corn cationic starch, graft copolymerization starch, Zulkovsky starch or tapioca (flour).
2, activated carbon for super capacitors according to claim 1, it is levied and is: described charing step is: get the starch of oven dry behind the moisture and place resistance furnace, be warming up to 350～550 ℃ under protection of inert gas, constant temperature 1～4h.
3, activated carbon for super capacitors according to claim 2, it is levied and is: described activation step is: the carbonized material grinding is mixed with the potassium hydroxide saturated solution, oven dry moisture is placed in the resistance furnace, is warming up to 750～850 ℃ under protection of inert gas, constant temperature 1～4h; Wherein, described carbonized material and potassium hydroxide solid weight proportion are 1: 4～8.
4, the preparation method of any one described activated carbon for super capacitors in the claim 1～3, its step is as follows:
1) starch is dried moisture; Described starch is oxidative crosslinked starch, corn cationic starch, graft copolymerization starch, Zulkovsky starch or tapioca (flour);
2) get the starch of oven dry behind the moisture and place resistance furnace, under protection of inert gas, be warming up to 350～550 ℃, constant temperature 1～4h, take out the cooling back, obtains carbonized material;
3) the carbonized material grinding is mixed with the potassium hydroxide saturated solution, oven dry moisture is placed in the resistance furnace, is warming up to 750～850 ℃ under protection of inert gas, constant temperature 1～4h, and the taking-up of cooling back grinds, and it is washed till neutrality, oven dry, promptly; Described carbonized material and potassium hydroxide solid weight proportion are 1: 4～8.
5, must ask the preparation method of 4 described activated carbon for super capacitors according to power, it is characterized in that: step 2) and step 3) in temperature rise rate be 1～5 ℃.
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|---|---|---|---|---|
| CN101950683A (en) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | Preparation method of semi-spherical active carbon electrode material of super capacitor |
| CN102354613A (en) * | 2011-09-14 | 2012-02-15 | 中国第一汽车股份有限公司 | Electrode material of supercapacitor and preparation method for electrode material |
| CN102689875A (en) * | 2012-06-11 | 2012-09-26 | 合肥工业大学 | Method for preparing microbiologically treated carbon material for supercapacitor |
| CN103641100A (en) * | 2013-12-17 | 2014-03-19 | 彭晓领 | Preparation method of cassava-starch-based grading-pore carbon microsphere material |
| CN103787321A (en) * | 2014-01-23 | 2014-05-14 | 广西师范大学 | Self-supporting graphene material and preparation method thereof |
| CN104085891A (en) * | 2014-07-14 | 2014-10-08 | 武汉大学 | Method for preparing carbon powder with high specific capacitance by using activated carbon activated by molten salt |
| CN104817065A (en) * | 2015-04-02 | 2015-08-05 | 安徽农业大学 | Preparation method of cellular starch-based porous carbon material |
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| CN105244178A (en) * | 2015-10-28 | 2016-01-13 | 王彦博 | Super capacitor and preparation method thereof |
| CN105948042A (en) * | 2016-05-06 | 2016-09-21 | 易电通（北京）储能科技有限公司 | Preparation method of activated carbon for supercapacitors |
| CN106345410A (en) * | 2016-09-30 | 2017-01-25 | 太原理工大学 | Carbon adsorbent for separating methane/nitrogen and preparation method of carbon adsorbent |
| CN107043109A (en) * | 2017-04-07 | 2017-08-15 | 南京正森环保科技有限公司 | A kind of preparation method of starch based super electric capacity absorbent charcoal material |
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| CN101950683A (en) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | Preparation method of semi-spherical active carbon electrode material of super capacitor |
| CN101950683B (en) * | 2010-09-09 | 2012-07-11 | 江西财经大学 | Preparation method of semi-spherical active carbon electrode material of super capacitor |
| CN102354613A (en) * | 2011-09-14 | 2012-02-15 | 中国第一汽车股份有限公司 | Electrode material of supercapacitor and preparation method for electrode material |
| CN102689875A (en) * | 2012-06-11 | 2012-09-26 | 合肥工业大学 | Method for preparing microbiologically treated carbon material for supercapacitor |
| CN103641100A (en) * | 2013-12-17 | 2014-03-19 | 彭晓领 | Preparation method of cassava-starch-based grading-pore carbon microsphere material |
| CN103787321A (en) * | 2014-01-23 | 2014-05-14 | 广西师范大学 | Self-supporting graphene material and preparation method thereof |
| CN104085891B (en) * | 2014-07-14 | 2016-06-08 | 武汉大学 | A kind of fused salt activated carbon prepares the method for high specific capacitance carbon dust |
| CN104085891A (en) * | 2014-07-14 | 2014-10-08 | 武汉大学 | Method for preparing carbon powder with high specific capacitance by using activated carbon activated by molten salt |
| CN104817065A (en) * | 2015-04-02 | 2015-08-05 | 安徽农业大学 | Preparation method of cellular starch-based porous carbon material |
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| CN105244178A (en) * | 2015-10-28 | 2016-01-13 | 王彦博 | Super capacitor and preparation method thereof |
| CN105948042A (en) * | 2016-05-06 | 2016-09-21 | 易电通（北京）储能科技有限公司 | Preparation method of activated carbon for supercapacitors |
| CN106345410B (en) * | 2016-09-30 | 2019-05-31 | 太原理工大学 | A kind of methane/nitrogen separation carbon adsorbent and preparation method thereof |
| CN106345410A (en) * | 2016-09-30 | 2017-01-25 | 太原理工大学 | Carbon adsorbent for separating methane/nitrogen and preparation method of carbon adsorbent |
| CN107043109A (en) * | 2017-04-07 | 2017-08-15 | 南京正森环保科技有限公司 | A kind of preparation method of starch based super electric capacity absorbent charcoal material |
| CN107043109B (en) * | 2017-04-07 | 2019-08-16 | 南京正森环保科技有限公司 | A kind of preparation method of starch based super capacitor absorbent charcoal material |
| CN110734061A (en) * | 2018-07-19 | 2020-01-31 | 深圳市环球绿地新材料有限公司 | super-capacity carbon, preparation method and application thereof |
| CN110734061B (en) * | 2018-07-19 | 2021-12-31 | 深圳市环球绿地新材料有限公司 | Super-capacity carbon, preparation method and application thereof |
| CN110877908A (en) * | 2018-09-06 | 2020-03-13 | 天津大学 | Preparation method of corn starch pyrolysis hard carbon electrode material |
| CN110482545A (en) * | 2019-09-04 | 2019-11-22 | 中国科学院山西煤炭化学研究所 | A kind of preparation method and its usage of high-crosslinking-degree starch |
| CN114380289A (en) * | 2021-12-13 | 2022-04-22 | 北方奥钛纳米技术有限公司 | Preparation method and application of carbonized particle material and activated carbon electrode material |
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