CN107275112B - Irradiation method prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material - Google Patents
Irradiation method prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a kind of irradiation methods to prepare MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, including：After bamboo charcoal is cleaned, drying；Bamboo charcoal after drying is added in manganese nitrate solution, antioxidant isopropanol is then added, obtains mixed liquor；Mixed liquor is ultrasonically treated 5~120min；By the mixed liquor sealing after ultrasound, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage is irradiated under conditions of being 50 1000kGy；Mixed liquor sample after irradiation is centrifuged, it is dry after being used in combination deionized water and ethyl alcohol to be respectively washed repeatedly, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.The preparation method of the present invention has the features such as operation is simple, and repeatability is strong, at low cost, environmentally safe.The MnO prepared using this method2The bamboo charcoal material of doping can effectively realize the Uniform Doped of bamboo charcoal as electrode material for super capacitor, this preparation method, to further increase ultracapacitor specific capacitance, enhance its cycle performance.
Description
Technical field
The invention belongs to field of material preparation, relate to a kind of using irradiation method preparation MnO2The method for adulterating bamboo charcoal, tool
Body is related to a kind of utilization60The gamma-ray irradiation that Co is generated is to prepare MnO2The bamboo charcoal of doping and its in ultracapacitor
The aspect application of electrode material.
Background technology
Ultracapacitor, also known as electrochemical capacitor, be grow up 70~eighties of 20th century one kind between battery
New type of energy storage device between traditional capacitor, have specific volume is big, power density is high, have extended cycle life with it is environmentally safe
The features such as.These features of ultracapacitor make it promise to be this century novel green energy resource, such as：As various storages
The stand-by power supply of device or the dynamical system etc. that composition electric vehicle is combined with battery.
According to the difference of energy storage mechnism, ultracapacitor can be divided into foundation on electrode/electrolyte interfacial electric double layer basis
On double layer capacitor and on the basis of establish the quick redox reaction of the high reversible occurred at electrode/electrolyte interface
Pseudocapacitors.The electrode material of double layer capacitor is mainly various high-specific surface area carbon materials, such as：Activated carbon, carbon nanometer
Pipe and carbon aerogels etc..Due to the price factor of carbon nanotube and carbon aerogels, activated carbon is obtained due to cheap
Widely apply.However the ultracapacitor specific volume of active carbon material is not generally high.Fake capacitance capacitor material is just like metal
Oxide (MnO2And RuO2Deng) and conducting polymer etc., there is higher specific capacity, but since its specific surface area is smaller, seriously
The dispersion for influencing active principle, to limit its application.
Using the advantage and disadvantage of two kinds of energy storage mechnism materials, people are conceived at present joins together to be applied to surpass by two kinds of materials
On grade capacitor.Current main synthetic method has chemical synthesis, such as sol-gal process, hydro-thermal method, the precipitation method to soak and set method etc.,
The major defect of chemical synthesis is to need to use a large amount of chemical reagent, so as to cause environmental pressure and manufacturing cost
It is higher；Another kind be physics synthetic method, that is, use simple physical mixed method, by metal oxide directly with active raw material of wood-charcoal
Material mixing, the method have the characteristics that it is simple and easy to operate, however the biggest problems are that doping unevenness.
The present invention combines the electrode material of double layer capacitor --- the large specific surface area and fake capacitance of activated carbon
Capacitor material MnO2High capacitance performance advantage, first passage irradiate synthetic method, it is only necessary to by γ irradiate a step,
The MnO of uniform doping can successfully be prepared2The active bamboo of load.And first passage the method prepares MnO2The work of load
Property bamboo charcoal, and obtained that specific capacitance is higher, recycled the excellent MnO of performance2The bamboo charcoal material of doping.
Invention content
In order to overcome the specific capacitance of current battery low, it is expensive the problems such as, the purpose of the present invention is to provide MnO2It mixes
Preparation method of the miscellaneous bamboo charcoal as electrode material for super capacitor.One easy steps is irradiated using γ, is prepared recyclable
Electrode material for super capacitor with long service life.The method of the present invention is simple with technological operation, repeatability is high, of low cost,
The features such as raw material sources are extensive.
It is excellent it is an object of the invention to solve at least the above and/or defect, and provide at least to will be described later
Point.
In order to realize these purposes and other advantages according to the present invention, a kind of irradiation method preparation MnO is provided2Doping
The method of bamboo charcoal based super capacitor electrode material, includes the following steps：
Step 1: after bamboo charcoal is cleaned with ethyl alcohol and deionized water respectively, 12~36 are dried at 80~120 DEG C of temperature
Hour；
Step 2: the bamboo charcoal after drying is added in manganese nitrate solution, antioxidant isopropanol is then added, is mixed
Feed liquid；Mixed liquor is ultrasonically treated 5~120min；
Step 3: the mixed liquor after ultrasound is sealed, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage
To be irradiated under conditions of 50-1000kGy；
Step 4: the mixed liquor sample after irradiation is centrifuged, deionized water and ethyl alcohol is used in combination to be respectively washed
It is dry after repeatedly, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.
Preferably, in the step 2, by weight, 0.01~10 part of bamboo charcoal, the nitre of 0.001~5mol/L is added
6~10 parts of sour manganese solution, 1~5 part of antioxidant isopropanol.
Preferably, in the step 2, further include before ultrasound：Mixed liquor is added in spherical container, by ball
It describes that device is placed on four axis bevellers, opens four axis bevellers, stainless steel spherical container is driven randomly to rotate, reaction 30~
60min；The feed inlet of the stainless steel spherical container is sealed by threaded cap, and threaded cap describes after being tightly connected with stainless steel ball
The surface of device flushes.
Preferably, the active rotating speed of the four axis beveller be 100~120rpm, the stochastic transition time be 30~
60s。
Preferably, which is characterized in that the power of the ultrasound is 200~800W, and frequency is 25~45kHz.
Preferably, the process of the ultrasound is：Mixed liquor is added in thermostat, sonde-type pulse ultrasonic wave is selected
Instrument is ultrasonically treated mixed liquor；5 under the probe insertion mixed liquor of the sonde-type pulse ultrasonic wave instrument~
10cm, it is 15~20s that the liquid level of mixed liquor, which keeps 12~15cm, burst length, and duty ratio is 60%~85%, permanent
Controlled at 20 DEG C in warm slot, the sound intensity is 200~500 W/cm2, 25~45kHz of supersonic frequency, processing time be 30~
60min；A diameter of 10mm of the probe.
Preferably, which is characterized in that in ultrasonication, nitrogen is passed through from bottom into mixed liquor；It is described
The flow velocity of nitrogen is 100-150mL/min.
Preferably, which is characterized in that the preparation method of the bamboo charcoal is：The bamboo of drying is placed in high temperature furnace,
Under argon gas protection, it is warming up to 500-1000 DEG C with 10-30 DEG C/min of heating rate, is carbonized 1-12 hours, grind into powder,
Obtain bamboo charcoal.
Preferably, which is characterized in that the bamboo further includes after following processing procedure will dry before being prepared into bamboo charcoal
Bamboo crush, be used in combination the sieve of 50~100 mesh, by weight, 5~10 parts of bamboo powder after being sieved is taken to be added to 60
In~100 parts of distilled water, lead to nitrogen protection, heating water bath stirs the mistake of 0.1~2 part of addition after 10-30min to 60~75 DEG C
Ammonium sulfate simultaneously stirs initiation 10-30min, and 10~20 parts of diallyldimethylammonium chlorides, the nitrogen at 60~80 DEG C is then added
Gas shielded reacts 2~4 hours, then uses ethanol precipitation, is dried in vacuo at 65 DEG C, is ground into powder up to pretreatment bamboo is arrived
Son；By weight, 30~50 parts of bamboo of pretreatment, 5~10 parts of octadecyldimethyl hydroxyethyl ammonium nitrate, sodium bicarbonate 3 are taken
~5 parts, 50~80 parts of water be added in the sealing containers of band stirring, being passed through nitrogen thereto makes nitrogen in feed liquid be saturated, then general
The sealing container, which is placed in the electron accelerator of 1.5MeV, 30mA, carries out irradiation stir process, then filters, dry, is made and changes
Property bamboo；For the radiation dose rate used that irradiates for 200~500kGy/h, irradiation dose is 500~2000kGy, stirring speed
Degree is 100~200r/min.
Preferably, which is characterized in that described dry using microwave radiation drying, process is：By the bamboo charcoal after cleaning
Material is put into quartzy drier, is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 50~100mL/min,
Microwave radiation drying process is carried out to precipitation；The condition that the microwave radiation is dried is：Microwave radiation frequencies be 2450 ±
50MHz, microwave radiation unit power are 0.10~1.00w/g, and microwave irradiation time is 30~60min, and microwave radiation temperature is
50~70 DEG C..
The present invention includes at least following advantageous effect：The present invention preparation method have operation is simple, repeatability
By force, at low cost, it is environmentally safe the features such as.The MnO prepared using this method2The bamboo charcoal material of doping is as ultracapacitor
Electrode material, this preparation method can effectively realize the Uniform Doped of bamboo charcoal, to further increase ultracapacitor specific capacitance
Amount, enhances its cycle performance.
Part is illustrated to embody by further advantage, target and the feature of the present invention by following, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Description of the drawings：
Fig. 1 is the MnO prepared in the embodiment of the present invention 12The bamboo charcoal material of doping is as electrode material for super capacitor
Charge and discharge specific capacitance figure；
Fig. 2 is the MnO prepared in embodiment 12The bamboo charcoal XPS collection of illustrative plates of doping；
Fig. 3 is that the C 1s of Fig. 2 XPS collection of illustrative plates absorb collection of illustrative plates；
Fig. 4 is that the Mn 2p of Fig. 2 XPS collection of illustrative plates absorb collection of illustrative plates；
Fig. 5 is that the O 1s of Fig. 2 XPS collection of illustrative plates absorb collection of illustrative plates；
Fig. 6 is the MnO prepared in the embodiment of the present invention 12The SEM of the bamboo charcoal of doping schemes；
Fig. 7 is the MnO prepared in the embodiment of the present invention 12The C element distribution map of the bamboo charcoal of doping；
Fig. 8 is the MnO prepared in the embodiment of the present invention 12The O distribution diagram of element of the bamboo charcoal of doping；
Fig. 9 is the MnO prepared in the embodiment of the present invention 12The Mn distribution diagram of element of the bamboo charcoal of doping.
Specific implementation mode：
Present invention will be described in further detail below with reference to the accompanying drawings, to enable those skilled in the art with reference to specification text
Word can be implemented according to this.
It should be appreciated that such as " having ", "comprising" and " comprising " term used herein do not allot one or more
The presence or addition of a other elements or combinations thereof.
Embodiment 1：
A kind of irradiation method preparation MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, includes the following steps：
Step 1: after bamboo charcoal is cleaned with ethyl alcohol and deionized water respectively, dried 12 hours at 80 DEG C of temperature；
Step 2: the 1g bamboo charcoals after drying are added in the manganese nitrate solution of a concentration of 0.1mol/L of 8mL, then it is added anti-
Oxidant isopropanol 2mL, obtains mixed liquor；Mixed liquor is put into the customization glass container that can be sealed, ultrasonic 30min；
Step 3: the mixed liquor after ultrasound is sealed, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage
To be irradiated under conditions of 1000kGy；
Step 4: the mixed liquor sample after irradiation is centrifuged, deionized water and ethyl alcohol is used in combination to be respectively washed
It is dry after repeatedly, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.
Fig. 2~5 are the MnO prepared in embodiment 12The bamboo charcoal XPS collection of illustrative plates of doping.As seen from Figure 1 sample mainly by
It is formed for C, Mn, O element.According to Fig. 4 MnO2642.4eV at combination can confirm Mn existence form be MnO2。
Fig. 6 is the MnO prepared in the embodiment of the present invention 12The bamboo charcoal SEM of doping, Fig. 7~9 are distribution diagram of element.By Fig. 6
It can be seen that MnO2It is evengranular to be distributed in bamboo charcoal surface.Fig. 7~9 are C, O, and Mn distribution diagram of element further demonstrates Mn's
In the presence of and distribution it is uniform.
Fig. 1 is the MnO prepared in the embodiment of the present invention 12The bamboo charcoal material of doping is as electrode material for super capacitor
Charge and discharge specific capacitance figure.As seen from Figure 3, under the current density of 1A/g, MnO2The bamboo charcoal material of doping discharges specific volume for the first time
Amount is 385F/g, and after 10000 cycles, specific capacitance remains to be maintained at 374F/g.It illustrates to be doped with MnO2Bamboo charcoal,
To which a kind of long, simple electrode material for super capacitor of preparation method with service life have successfully been obtained.
Embodiment 2：
A kind of irradiation method preparation MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, includes the following steps：
Step 1: after bamboo charcoal is cleaned with ethyl alcohol and deionized water respectively, dried 12 hours at 80 DEG C of temperature；
Step 2: the 1g bamboo charcoals after drying are added in the manganese nitrate solution of a concentration of 0.1mol/L of 8mL, then it is added anti-
Oxidant isopropanol 2mL, obtains mixed liquor；Mixed liquor is put into the customization glass container that can be sealed, ultrasonic 30min；
Step 3: the mixed liquor after ultrasound is sealed, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage
To be irradiated under conditions of 500kGy；
Step 4: the mixed liquor sample after irradiation is centrifuged, deionized water and ethyl alcohol is used in combination to be respectively washed
It is dry after repeatedly, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.Under the current density of 1A/g, the MnO2It mixes
Miscellaneous bamboo charcoal material first discharge specific capacity is 384F/g, and after 10000 cycles, specific capacitance remains to be maintained at 373F/
g。
Embodiment 3：
A kind of irradiation method preparation MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, includes the following steps：
Step 1: after bamboo charcoal is cleaned with ethyl alcohol and deionized water respectively, dried 12 hours at 80 DEG C of temperature；
Step 2: the 1g bamboo charcoals after drying are added in the manganese nitrate solution of a concentration of 1mol/L of 8mL, antioxygen is then added
Agent isopropanol 2mL, obtains mixed liquor；Mixed liquor is put into the customization glass container that can be sealed, ultrasonic 30min；
Step 3: the mixed liquor after ultrasound is sealed, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage
To be irradiated under conditions of 1000kGy；
Step 4: the mixed liquor sample after irradiation is centrifuged, deionized water and ethyl alcohol is used in combination to be respectively washed
It is dry after repeatedly, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.Under the current density of 1A/g, the MnO2It mixes
Miscellaneous bamboo charcoal material first discharge specific capacity is 386F/g, and after 10000 cycles, specific capacitance remains to be maintained at 376F/
g。
Embodiment 4：
A kind of irradiation method preparation MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, includes the following steps：
Step 1: after bamboo charcoal is cleaned with ethyl alcohol and deionized water respectively, dried 12 hours at 80 DEG C of temperature；
Step 2: the 1g bamboo charcoals after drying are added in the manganese nitrate solution of a concentration of 0.2mol/L of 8mL, then it is added anti-
Oxidant isopropanol 2mL, obtains mixed liquor；Mixed liquor is put into the customization glass container that can be sealed, ultrasonic 30min；
Step 3: the mixed liquor after ultrasound is sealed, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage
To be irradiated under conditions of 1000kGy；
Step 4: the mixed liquor sample after irradiation is centrifuged, deionized water and ethyl alcohol is used in combination to be respectively washed
It is dry after repeatedly, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.Under the current density of 1A/g, the MnO2It mixes
Miscellaneous bamboo charcoal material first discharge specific capacity is 385F/g, and after 10000 cycles, specific capacitance remains to be maintained at 376F/
g。
Embodiment 5：
A kind of irradiation method preparation MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, includes the following steps：
Step 1: after bamboo charcoal is cleaned with ethyl alcohol and deionized water respectively, dried 24 hours at 80 DEG C of temperature；
Step 2: by weight, 1 part of bamboo charcoal after drying is added in the manganese nitrate solution of 10 parts of a concentration of 1mol/L,
Then 2 parts of antioxidant isopropanol is added, obtains mixed liquor；By mixed liquor, ultrasonic 30min；The power of the ultrasound is
500W, frequency 30kHz；
Step 3: the mixed liquor after ultrasound is sealed, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage
To be irradiated under conditions of 1000kGy；
Step 4: the mixed liquor sample after irradiation is centrifuged, deionized water and ethyl alcohol is used in combination to be respectively washed
It is dry after repeatedly, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.Under the current density of 1A/g, the MnO2It mixes
Miscellaneous bamboo charcoal material first discharge specific capacity is 388F/g, and after 10000 cycles, specific capacitance remains to be maintained at 379F/
g。
Embodiment 6：
In the step 2, further include before ultrasound：Mixed liquor is added in spherical container, spherical container is placed in
On four axis bevellers, four axis bevellers are opened, stainless steel spherical container is driven randomly to rotate, react 60min；The stainless steel ball
Describe that the feed inlet of device is sealed by threaded cap, threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；It is described
The active rotating speed of four axis bevellers is 100rpm, and the stochastic transition time is 60s.Remaining technological parameter and process and embodiment 5
In it is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 395F/g, warp
After crossing 10000 cycles, specific capacitance remains to be maintained at 388F/g.The present invention carries spherical container by four axis bevellers, real
Random rotation solidification in existing spherical container.Sealing spherical container is consolidated by four support shafts of four axis bevellers
It is fixed, the change-over period between four axis slewing rates and active and driven shaft is adjusted, realizes that the trackless in additional flow field is orientated.The party
Method keeps the mixing of bamboo charcoal and manganese nitrate more uniform, improves the efficiency of irradiation synthetic reaction, makes MnO2Doping it is more equal
It is even.
Embodiment 7：
In the step 2, further include before ultrasound：Mixed liquor is added in spherical container, spherical container is placed in
On four axis bevellers, four axis bevellers are opened, stainless steel spherical container is driven randomly to rotate, react 45min；The stainless steel ball
Describe that the feed inlet of device is sealed by threaded cap, threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；It is described
The active rotating speed of four axis bevellers is 150rpm, and the stochastic transition time is 30s.Remaining technological parameter and process and embodiment 5
In it is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 394F/g,
After 10000 cycles, specific capacitance remains to be maintained at 387F/g.
Embodiment 8：
The process of the ultrasound is：Mixed liquor is added in thermostat, selects sonde-type pulse ultrasonic wave instrument to mixed
Feed liquid is closed to be ultrasonically treated；The probe of the sonde-type pulse ultrasonic wave instrument is inserted into 10cm under mixed liquor, mixed liquor
Liquid level keep the 15cm, burst length 20s, duty ratio 80% to be controlled at 20 DEG C, the sound intensity in thermostat
200W/cm2, supersonic frequency 45kHz, processing time 60min；A diameter of 10mm of the probe.Remaining technological parameter and mistake
Journey with it is identical in embodiment 5.Under the current density of 1A/g, the MnO2The bamboo charcoal material of doping discharges specific volume for the first time
Amount is 396F/g, and after 10000 cycles, specific capacitance remains to be maintained at 389F/g.
Embodiment 9：
The process of the ultrasound is：Mixed liquor is added in thermostat, selects sonde-type pulse ultrasonic wave instrument to mixed
Feed liquid is closed to be ultrasonically treated；The probe of the sonde-type pulse ultrasonic wave instrument is inserted into 5cm under mixed liquor, mixed liquor
Liquid level keeps the 10cm, burst length 15s, duty ratio 75% to be controlled at 20 DEG C, the sound intensity in thermostat
300W/cm2, supersonic frequency 30kHz, processing time 40min；A diameter of 10mm of the probe.Remaining technological parameter and mistake
Journey with it is identical in embodiment 5.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping
For 397F/g, after 10000 cycles, specific capacitance remains to be maintained at 390F/g.
Embodiment 10：
In ultrasonication, nitrogen is passed through from bottom into mixed liquor；The flow velocity of the nitrogen is 100mL/
min.Remaining technological parameter and process with it is identical in embodiment 8.Under the current density of 1A/g, the MnO2The bamboo of doping
Carbon Materials first discharge specific capacity is 401F/g, and after 10000 cycles, specific capacitance remains to be maintained at 395F/g.
Embodiment 11：
In ultrasonication, nitrogen is passed through from bottom into mixed liquor；The flow velocity of the nitrogen is 120mL/
min.Remaining technological parameter and process with it is identical in embodiment 9.Under the current density of 1A/g, the MnO2The bamboo of doping
Carbon Materials first discharge specific capacity is 402F/g, and after 10000 cycles, specific capacitance remains to be maintained at 396F/g.
Embodiment 12：
The preparation method of the bamboo charcoal is：The bamboo of drying is placed in high temperature furnace, under protection of argon gas, with 30 DEG C/minute
The heating rate of clock is warming up to 800 DEG C, carbonizes 12 hours, grind into powder obtains bamboo charcoal.Remaining technological parameter and process and reality
It applies identical in example 5.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is
393F/g, after 10000 cycles, specific capacitance remains to be maintained at 385F/g.
Embodiment 13：
The preparation method of the bamboo charcoal is：The bamboo of drying is placed in high temperature furnace, under protection of argon gas, with 15 DEG C/minute
The heating rate of clock is warming up to 1000 DEG C, carbonizes 6 hours, grind into powder obtains bamboo charcoal.Remaining technological parameter and process and reality
It applies identical in example 5.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is
392F/g, after 10000 cycles, specific capacitance remains to be maintained at 384F/g.
Embodiment 14：
The bamboo further includes that following processing procedure crushes the bamboo after drying, 100 mesh is used in combination before being prepared into bamboo charcoal
Sieve, by weight, take sieving after 10 parts of bamboo powder be added in 100 parts of distilled water, lead to nitrogen protection, water-bath
75 DEG C are heated to, 2 parts of ammonium persulfate is added after stirring 30min and stirs initiation 30min, 20 parts of diallyls two are then added
Ammonio methacrylate, nitrogen protection is reacted 4 hours at 80 DEG C, is then used ethanol precipitation, is dried in vacuo, is crushed into powder at 65 DEG C
End obtains pretreatment bamboo；By weight, take pretreatment 50 parts of bamboo, 10 parts of octadecyldimethyl hydroxyethyl ammonium nitrate,
5 parts of sodium bicarbonate, 80 parts of water are added in the sealing container with stirring, and being passed through nitrogen thereto makes nitrogen in feed liquid be saturated, then
The sealing container is placed in the electron accelerator of 1.5MeV, 30mA and carries out irradiation stir process, is then filtered, it is dry, it is made
Modified bamboo；The radiation dose rate used that irradiates is 200kGy/h, irradiation dose 600kGy, mixing speed 200r/
min.Remaining technological parameter and process with it is identical in embodiment 12.Under the current density of 1A/g, the MnO2Doping
Bamboo charcoal material first discharge specific capacity is 403F/g, and after 10000 cycles, specific capacitance remains to be maintained at 397F/g.It is logical
The modification for crossing the process makes bamboo form more pore structures, and introduces new chemical group, after high temperature cabonization, improves
The specific surface area of bamboo charcoal, keeps the mixing of bamboo charcoal and manganese nitrate more uniform, makes MnO2Doping it is more uniform.
Embodiment 15：
The bamboo further includes that following processing procedure crushes the bamboo after drying, 100 mesh is used in combination before being prepared into bamboo charcoal
Sieve take 5 parts of bamboo powder after sieving to be added in 60 parts of distilled water by weight, lead to nitrogen protection, water-bath adds
Heat is added 0.2 part of ammonium persulfate after stirring 20min and stirs initiation 10min, 20 parts of diallyls two are then added to 70 DEG C
Ammonio methacrylate, nitrogen protection is reacted 4 hours at 80 DEG C, is then used ethanol precipitation, is dried in vacuo, is crushed into powder at 65 DEG C
End obtains pretreatment bamboo；By weight, take pretreatment 50 parts of bamboo, 10 parts of octadecyldimethyl hydroxyethyl ammonium nitrate,
5 parts of sodium bicarbonate, 80 parts of water are added in the sealing container with stirring, and being passed through nitrogen thereto makes nitrogen in feed liquid be saturated, then
The sealing container is placed in the electron accelerator of 1.5MeV, 30mA and carries out irradiation stir process, is then filtered, it is dry, it is made
Modified bamboo；The radiation dose rate used that irradiates is 500kGy/h, irradiation dose 2000kGy, mixing speed 200r/
min.Remaining technological parameter and process with it is identical in embodiment 13.Under the current density of 1A/g, the MnO2Doping
Bamboo charcoal material first discharge specific capacity is 404F/g, and after 10000 cycles, specific capacitance remains to be maintained at 398F/g.
Embodiment 16：
Described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 100mL/min, precipitation is carried out at microwave radiation drying
Reason；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
1.00w/g, microwave irradiation time 60min, microwave radiation temperature are 70 DEG C.In remaining technological parameter and process and embodiment 5
It is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 397F/g, warp
After crossing 10000 cycles, specific capacitance remains to be maintained at 390F/g.It is dried using microwave radiation, microwave is in heating object
What portion generated, heat source comes from interior of articles, and homogeneous heating is conducive to improve bamboo charcoal material quality, simultaneously because inside and outside adding simultaneously
Heat substantially reduces heating time, and the efficiency of heating surface is high, is conducive to improve bamboo charcoal material yield, the bamboo charcoal base being had excellent performance is super
Grade capacitor electrode material.
Embodiment 17：
Described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 100mL/min, precipitation is carried out at microwave radiation drying
Reason；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
1.00w/g, microwave irradiation time 60min, microwave radiation temperature are 60 DEG C.In remaining technological parameter and process and embodiment 7
It is identical.Remaining technological parameter and process with it is identical in embodiment 5.Under the current density of 1A/g, the MnO2
The bamboo charcoal material first discharge specific capacity of doping is 407F/g, and after 10000 cycles, specific capacitance remains to be maintained at
400F/g。
Embodiment 18：
Described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 100mL/min, precipitation is carried out at microwave radiation drying
Reason；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
1.00w/g, microwave irradiation time 60min, microwave radiation temperature are 60 DEG C.In remaining technological parameter and process and embodiment 9
It is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 408F/g, warp
After crossing 10000 cycles, specific capacitance remains to be maintained at 402F/g.
Embodiment 19：
Described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 100mL/min, precipitation is carried out at microwave radiation drying
Reason；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
1.00w/g, microwave irradiation time 60min, microwave radiation temperature are 60 DEG C.In remaining technological parameter and process and embodiment 11
It is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 412F/g, warp
After crossing 10000 cycles, specific capacitance remains to be maintained at 406F/g.
Embodiment 20:
Described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 100mL/min, precipitation is carried out at microwave radiation drying
Reason；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
1.00w/g, microwave irradiation time 60min, microwave radiation temperature are 60 DEG C.In remaining technological parameter and process and embodiment 13
It is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 406F/g, warp
After crossing 10000 cycles, specific capacitance remains to be maintained at 399F/g.
Embodiment 21：
Described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 100mL/min, precipitation is carried out at microwave radiation drying
Reason；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
1.00w/g, microwave irradiation time 60min, microwave radiation temperature are 60 DEG C.In remaining technological parameter and process and embodiment 15
It is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 414F/g, warp
After crossing 10000 cycles, specific capacitance remains to be maintained at 409F/g.
Embodiment 22：
In the step 2, further include before ultrasound：Mixed liquor is added in spherical container, spherical container is placed in
On four axis bevellers, four axis bevellers are opened, stainless steel spherical container is driven randomly to rotate, react 60min；The stainless steel ball
Describe that the feed inlet of device is sealed by threaded cap, threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；It is described
The active rotating speed of four axis bevellers is 100rpm, and the stochastic transition time is 60s.Remaining technological parameter and process and embodiment 9
In it is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 408F/g,
After 10000 cycles, specific capacitance remains to be maintained at 402F/g.
Embodiment 23：
In the step 2, further include before ultrasound：Mixed liquor is added in spherical container, spherical container is placed in
On four axis bevellers, four axis bevellers are opened, stainless steel spherical container is driven randomly to rotate, react 60min；The stainless steel ball
Describe that the feed inlet of device is sealed by threaded cap, threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；It is described
The active rotating speed of four axis bevellers is 100rpm, and the stochastic transition time is 60s.Remaining technological parameter and process and embodiment
It is identical in 11.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 412F/
G, after 10000 cycles, specific capacitance remains to be maintained at 405F/g.
Embodiment 24：
In the step 2, further include before ultrasound：Mixed liquor is added in spherical container, spherical container is placed in
On four axis bevellers, four axis bevellers are opened, stainless steel spherical container is driven randomly to rotate, react 60min；The stainless steel ball
Describe that the feed inlet of device is sealed by threaded cap, threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；It is described
The active rotating speed of four axis bevellers is 100rpm, and the stochastic transition time is 60s.Remaining technological parameter and process and embodiment
It is identical in 13.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 406F/
G, after 10000 cycles, specific capacitance remains to be maintained at 401F/g.
Embodiment 25：
In the step 2, further include before ultrasound：Mixed liquor is added in spherical container, spherical container is placed in
On four axis bevellers, four axis bevellers are opened, stainless steel spherical container is driven randomly to rotate, react 60min；The stainless steel ball
Describe that the feed inlet of device is sealed by threaded cap, threaded cap flushes after being tightly connected with the surface of stainless steel spherical container；It is described
The active rotating speed of four axis bevellers is 100rpm, and the stochastic transition time is 60s.Remaining technological parameter and process and embodiment
It is identical in 15.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 413F/
G, after 10000 cycles, specific capacitance remains to be maintained at 408F/g.
Embodiment 26：
The process of the ultrasound is：Mixed liquor is added in thermostat, selects sonde-type pulse ultrasonic wave instrument to mixed
Feed liquid is closed to be ultrasonically treated；The probe of the sonde-type pulse ultrasonic wave instrument is inserted into 5cm under mixed liquor, mixed liquor
Liquid level keeps the 10cm, burst length 15s, duty ratio 75% to be controlled at 20 DEG C, the sound intensity in thermostat
300W/cm2, supersonic frequency 30kHz, processing time 40min；A diameter of 10mm of the probe.Remaining technological parameter and mistake
Journey with it is identical in embodiment 13.Under the current density of 1A/g, the MnO2The bamboo charcoal material of doping discharges specific volume for the first time
Amount is 407F/g, and after 10000 cycles, specific capacitance remains to be maintained at 401F/g.
Embodiment 27：
The process of the ultrasound is：Mixed liquor is added in thermostat, selects sonde-type pulse ultrasonic wave instrument to mixed
Feed liquid is closed to be ultrasonically treated；The probe of the sonde-type pulse ultrasonic wave instrument is inserted into 5cm under mixed liquor, mixed liquor
Liquid level keeps the 10cm, burst length 15s, duty ratio 75% to be controlled at 20 DEG C, the sound intensity in thermostat
300W/cm2, supersonic frequency 30kHz, processing time 40min；A diameter of 10mm of the probe.Remaining technological parameter and mistake
Journey with it is identical in embodiment 15.Under the current density of 1A/g, the MnO2The bamboo charcoal material of doping discharges specific volume for the first time
Amount is 415F/g, and after 10000 cycles, specific capacitance remains to be maintained at 409F/g.
Embodiment 28：
Described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 100mL/min, precipitation is carried out at microwave radiation drying
Reason；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, and microwave radiation unit power is
1.00w/g, microwave irradiation time 60min, microwave radiation temperature are 60 DEG C.In remaining technological parameter and process and embodiment 27
It is identical.Under the current density of 1A/g, the MnO2The bamboo charcoal material first discharge specific capacity of doping is 425F/g, warp
After crossing 10000 cycles, specific capacitance remains to be maintained at 419F/g.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and legend shown and described herein.
Claims (10)
1. a kind of irradiation method prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, which is characterized in that including following
Step：
Step 1: after bamboo charcoal is cleaned with ethyl alcohol and deionized water respectively, dried 12~36 hours at 80~120 DEG C of temperature；
Step 2: the bamboo charcoal after drying is added in manganese nitrate solution, antioxidant isopropanol is then added, obtains mixture
Liquid；Mixed liquor is ultrasonically treated 5~120min；
Step 3: the mixed liquor after ultrasound is sealed, and mixed liquor is placed in60In the gamma-rays that Co is generated, dosage 50-
It is irradiated under conditions of 1000kGy；
Step 4: the mixed liquor sample after irradiation is centrifuged, deionized water and ethyl alcohol is used in combination to be respectively washed repeatedly
Afterwards, dry, obtain MnO2Adulterate bamboo charcoal based super capacitor electrode material.
2. irradiation method as described in claim 1 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, feature
It is, in the step 2, by weight, 0.01~10 part of bamboo charcoal, the manganese nitrate solution 6~10 of 0.001~5mol/L is added
Part, 1~5 part of antioxidant isopropanol.
3. irradiation method as described in claim 1 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, feature
It is, in the step 2, further includes before ultrasound：Mixed liquor is added in spherical container, spherical container is placed in four
On axis beveller, four axis bevellers are opened, stainless steel spherical container is driven randomly to rotate, react 30~60min；The stainless steel
The feed inlet of spherical container is sealed by threaded cap, and threaded cap flushes after being tightly connected with the surface of stainless steel spherical container.
4. irradiation method as claimed in claim 3 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, described four
The active rotating speed of axis beveller is 100~120rpm, and the stochastic transition time is 30~60s.
5. irradiation method as described in claim 1 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, feature
It is, the power of the ultrasound is 200~800W, and frequency is 25~45kHz.
6. irradiation method as described in claim 1 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material is described super
The process of sound is：Mixed liquor is added in thermostat, sonde-type pulse ultrasonic wave instrument is selected to carry out ultrasound to mixed liquor
Processing；The probe of the sonde-type pulse ultrasonic wave instrument is inserted into 5~10cm under mixed liquor, and the liquid level of mixed liquor is protected
12~15cm is held, the burst length is 15~20s, and duty ratio is 60%~85%, is controlled at 20 DEG C, the sound intensity in thermostat
200~500W/cm2, 25~45kHz of supersonic frequency, processing time is 30~60min；A diameter of 10mm of the probe.
7. irradiation method as claimed in claim 6 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, feature
It is, in ultrasonication, nitrogen is passed through from bottom into mixed liquor；The flow velocity of the nitrogen is 100-150mL/
min。
8. irradiation method as described in claim 1 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, feature
It is, the preparation method of the bamboo charcoal is：The bamboo of drying is placed in high temperature furnace, under protection of argon gas, with 10-30 DEG C/minute
The heating rate of clock is warming up to 500-1000 DEG C, carbonizes 1-12 hours, grind into powder obtains bamboo charcoal.
9. irradiation method as claimed in claim 8 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, feature
It is, the bamboo further includes that following processing procedure crushes the bamboo after drying, be used in combination 50~100 before being prepared into bamboo charcoal
Purpose sieve takes 5~10 parts of bamboo powder after sieving to be added in 60~100 parts of distilled water by weight, leads to nitrogen
Protection, heating water bath are added 0.1~2 part of ammonium persulfate after stirring 10-30min and stir initiation 10- to 60~75 DEG C
10~20 parts of diallyldimethylammonium chlorides are then added in 30min, and nitrogen protection is reacted 2~4 hours at 60~80 DEG C,
Then ethanol precipitation is used, is dried in vacuo at 65 DEG C, is ground into powder up to pretreatment bamboo is arrived；By weight, pretreatment is taken
50~80 parts of 30~50 parts of bamboo, 5~10 parts of octadecyldimethyl hydroxyethyl ammonium nitrate, 3~5 parts of sodium bicarbonate, water additions
In sealing container with stirring, being passed through nitrogen thereto makes in feed liquid nitrogen be saturated, then by the sealing container be placed in 1.5MeV,
Irradiation stir process is carried out in the electron accelerator of 30mA, is then filtered, it is dry, modified bamboo is made；What the irradiation used
Radiation dose rate is 200~500kGy/h, and irradiation dose is 500~2000kGy, and mixing speed is 100~200r/min.
10. irradiation method as described in claim 1 prepares MnO2The method for adulterating bamboo charcoal based super capacitor electrode material, it is special
Sign is that described dry using microwave radiation drying, process is：Bamboo charcoal material after cleaning is put into quartzy drier,
It is subsequently placed in microwave radiation reacting furnace；It is passed through nitrogen with the speed of 50~100mL/min, microwave radiation drying is carried out to precipitation
Processing；The condition that the microwave radiation is dried is：Microwave radiation frequencies are 2450 ± 50MHz, microwave radiation unit power
For 0.10~1.00w/g, microwave irradiation time is 30~60min, and microwave radiation temperature is 50~70 DEG C.
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| CN111554515B (en) * | 2020-05-11 | 2021-12-21 | 深圳美诺克科技有限公司 | MnO (MnO)2Supercapacitor electrode material for modifying biomass porous carbon and preparation method thereof |
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