Background technology
The ultracapacitor that grew up had in recent years both had the high-specific-power and the cyclicity of conventional physical electric capacity, had the high-energy-density characteristic of chemical power source again, the working conditions of high-specific-power so it can meet the demands, the working conditions of the high-energy-density that can meet the demands again.Because ultracapacitor has the large vol energy-storage property that good pulse charge-discharge performance and conventional physical electric capacity are not had, the application in high energy pulse laser has caused people's extensive concern.Simultaneously, because of its stored energy is big, light weight, can unlimited discharging and recharging and by people as the unify standby power supply of telecommunication equipment of department of computer science.Along with the rise of environmental-protecting type electric automotive research, ultracapacitor can independently or with secondary cell (like lead-acid cell or lithium ion battery) make up the power-supply system as electromobile, and prospect is widely used.
The energy storage of ultracapacitor is based on the electrostatic double layer that electrode charges and forms down, therefore requires the material of electrode should have very high specific surface area and suitable big density.Gac is because of having higher specific surface area, wide material sources and advantage such as cheap receives people's concern widely.Wildwood is main source in all raw materials of preparation gac, but along with the enforcement of wildwood protected project, domestic timber yield falls sharply, and wooden carbon source can not satisfy the particularly needs of high-tech develop rapidly of national economy fast development.Under the background of " people-oriented; Sustainable development ", bamboo resource because of with short production cycle, reproduction speed is fast, carbon content is high, sulphur content and ash oontent are extremely low; Have very high specific surface area and electroconductibility, receive in the supercapacitor applications field widely and paying close attention to.But traditional method is produced gac, long reaction time, energy consumption is high, activator level is big, production cost is high, seriously polluted, the gac electric capacity of producing is not high.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of active carbon electrode material for super capacitor, overcome present active carbon electrode material preparation method cost height, with serious pollution problem, improve the electric capacity of material simultaneously.
The technical scheme that the present invention adopts is following:
The preparation method of active carbon electrode material for super capacitor, with exsiccant bamboo bits carry out successively that alkali soaks, microwave activation, pickling, washing, microwave irradiation power is 100-1000W during microwave activation, time 10-20min, temperature 650-750 ℃.
Alkali carries out gamma-ray irradiation earlier before soaking step, and irradiation adopts
60The Co gamma ray projector, radiation dose rate 2.6 * 10
3Gy/h, irradiation dose are 50-50000Gy.
Concrete, it is 1-15mm that bamboo powder is broken to length, at 100-120 ℃ of dry 1-2h.
When alkali soaks dried bamboo bits being placed mass concentration is that the potassium hydroxide solution of 10-30% soaks 10-48h, and the mass ratio that Pottasium Hydroxide and bamboo are considered to be worth doing in the solution is 1-5:1.
Cool off behind the microwave activation, the aqueous hydrochloric acid immersion 4-8h of mass concentration as 5-10% used in the washing back.
More concrete, step is following:
1) bamboo powder being broken to length is 1-15mm, then dry 1-2h under 100-120 ℃ of temperature;
2) raw material that step 1) is obtained adopts gamma ray projector irradiation, and the actual conditions of irradiation is to adopt
60The Co gamma ray projector, radiation dose rate 2.6 * 10
3Gy/h, irradiation dose are 50-50000Gy;
3) with step 2) to place mass concentration be that the potassium hydroxide solution of 10-30% soaks 10-48h for the raw material that obtains, and the mass ratio of Pottasium Hydroxide and bamboo wood is 1-5:1, and it is 98% technical grade Pottasium Hydroxide that Pottasium Hydroxide can be selected purity;
4) mixture after the filtration that step 3) is obtained carries out microwave activation, and microwave irradiation power is 100-1000W, microwave irradiation time 10-20min, temperature of reaction 650-750 ℃;
5) the cooled product that step 4) is obtained is used distilled water flushing, reclaims excessive Pottasium Hydroxide, then adopts the technical hydrochloric acid aqueous solution of 5-10% to carry out the immersion of 4-8h;
6) product that step 5) is obtained reaches neutral with distilled water flushing to pH value, and oven dry promptly obtains said active carbon electrode material for super capacitor.
The present invention is intended to improve the electric capacity of material, and emphasis is from increasing the gac specific surface area, improve wherein porosity, being started with in its surface-treated aspect and improve its electric capacity.
When adopting microwave activation in the method, mainly be to cause the heating of mao bamboon and acvator through microwave, and make it to react that generate active carbon with high specific surface area, preparation cycle is short, energy consumption is low; Adopt
60The Co gamma-rays carries out irradiation to charcoal source mao bamboon, and the strong penetrance of ray can be broken the cell walls of mao bamboon, makes alkali activator be easy to be immersed in the mao bamboon cell interior equably, and the high-energy of ray makes the more activated point of the inner formation in charcoal source.Simultaneously, introduce oxygen-containing functional group at activated carbon surface, the wellability of raw material of wood-charcoal material is strengthened, resistance reduces, and the effect of fake capacitance also can make the electric capacity of gac improve.
The present invention has following advantage with respect to prior art:
1, be raw material with bamboo wood and bamboo processing waste, cheap, wide material sources had both helped waste ' s reclamation and environment protection, also can reduce the manufacturing cost of gac;
2, utilize microwave can be directly to the heating of material inside, make that gac is inner to produce a large amount of active sites, homogeneous heating, speed is fast, the time spent is few, activation temperature is low, energy consumption is low, is that heating source prepares gac and can effectively promote gac pore-creating with it;
3, adopt gamma-ray irradiation bamboo bits, the amount of having saved acvator has reduced cost, and the gac many-side has been carried out modification, has improved the electric capacity of gac, clean and effective;
4, few, simple to operate, the environmentally safe of present method facility investment, be easy to accomplish scale production.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1-5
To 1-15mm, 100 ℃ of dry 2h adopt the irradiation gamma ray source with bamboo processing waste breaking length
60Co, radiation dose rate 2.6 * 10
3Gy/h, irradiation dose are 10000Gy, and then using mass concentration is 30% potassium hydroxide solution dipping 24h; Alkali carbonaceous amount ratio is respectively 1:1,2:1,3:1,4:1,5:1, in the microwave oven of packing into, in power 700W microwave 12min; Take out the salt soak 4h that adopts washing, 10% (wt%), and after washing to neutrality, 100 ℃ of oven dry in baking oven; Be crushed to-400 orders again, obtain gac.Gac with embodiment 1-5 is that material prepn becomes ultracapacitor, is electrolytic solution with 30% (wt%) KOH aqueous solution, and the charging/discharging voltage scope is at 0.05-1.0V, and charging and discharging currents is 300mA/g, and corresponding data is seen table 1.
Embodiment 6-9
It is 1-15mm that the bamboo processing waste is crushed to length, and 110 ℃ of dry 1.5h adopt the irradiation gamma ray source
60Co, radiation dose rate 2.6 * 10
3Gy/h, irradiation dose are 30000Gy, and then using concentration is 30% potassium hydroxide solution dipping 48h, and alkali charcoal mass ratio is 3:1, in the microwave oven of packing into, is respectively microwave 12min under 200W, 400W, 700W, the 900W at power, takes out the back step with embodiment 1-5.Corresponding data is seen table 2.
Embodiment 10-13
It is 1-15mm that the bamboo processing waste is crushed to length, and 120 ℃ of dry 1h adopt the irradiation gamma ray source
60Co, radiation dose rate 2.6 * 10
3Gy/h, irradiation dose are 50000Gy, and then using concentration is 30% potassium hydroxide solution dipping 10h, and alkali charcoal mass ratio is 3:1, and microwave 10min, 12min, 15min, 20min respectively under power 700W take out afterwards step with embodiment 1-5.Corresponding data is seen table 3.
Comparative Examples 1
It is 1-15mm that the bamboo processing waste is crushed to length, and behind 120 ℃ of dry 1h, use concentration is 30% potassium hydroxide solution dipping 48h, and alkali charcoal mass ratio is 3:1, in the microwave oven of packing into, is microwave 12min under the 900W at power, takes out the back step with embodiment 1-5.Test result shows: the gac specific storage is 295.5 F/g.The specific storage that embodiment 9 obtains gac is 360.7 F/g, compares without the material of irradiation with this example, and capacity has improved 22.1% behind the irradiation.
Comparative Examples 2
Adopt traditional pyroprocess to prepare gac: it is 1-15mm that the bamboo processing waste is crushed to length, N
2After the following 400 ℃ of charings of atmosphere with the ratio uniform mixing of 30%KOH according to 1:5, N afterwards
2Protect following 800 ℃ of activation 5h, and after washing, pickling, washing is to neutral once more.Electrochemical property test is the same.Test result shows: the gac specific storage is 290.5F/g, than the low 70.2F/g of embodiment 9 capacity 360.7F/g.