CN109830376A - The method that additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material - Google Patents
The method that additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material Download PDFInfo
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Abstract
The present invention provides a kind of method that additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material, the activation of two step of alkali-acid first is carried out to submicron order bamboo charcoal, again using bamboo charcoal, metal salt and urea as raw material, successively by oxidation step in outer power-up, the hydro-thermal reaction in magnetic field and air, the combination electrode material with height ratio capacity and high circulation stability is prepared.The method of the present invention raw material are cheap and easy to get, at low cost, simple and easy, favorable reproducibility, and the metal oxide agglomeration of additional electromagnetic field auxiliary preparation, which improves obvious, prepared combination electrode material, has very high specific capacity and cyclical stability；The method of the present invention has a extensive future in fields such as the preparations of electrode material for super capacitor.
Description
Technical field
The present invention relates to a kind of preparation methods of electrode material to answer more particularly to a kind of method of combination electrode material
For technical field of energy material or biomass composite technical field.
Background technique
With the fast development of global economy, non-renewable fossil energy is largely consumed, and causes serious dirt to environment
Dye.Exploitation cleaning, reproducible energy-storage system are extremely urgent.In various energy storage devices, electrochemical energy storage is flexible because of it
Property, high efficiency and the features such as diversification and and be concerned, mainly include lithium ion battery, lead storage battery, fuel cell, hydrogen nickel
Battery and supercapacitor etc..Wherein lithium ion battery, lead storage battery, fuel cell and Ni-H cell are directed to ultra high power density
When charge and discharge, since the heat of fast electrochemical reaction releasing and the structure change of active material can make battery bear very big pressure
Power and security risk, the problem of being easy to cause its inefficient and secure context.And supercapacitor is between traditional capacitor and to fill
A kind of new and effective energy storage device between battery, is making up lithium ion battery, lead storage battery, fuel cell and Ni-H cell
While the defects of power density is low, cycle life is poor, high rate during charging-discharging is poor, fast charging and discharging is realized, and recycle effect
Rate is high, has extended cycle life, is environmental-friendly, is safe, all has in fields such as new energy, electronics industry, electric car, defence and militaries
Wide application value.
Electrode material plays an important role to its overall performance as the most important component part of supercapacitor.At present
The electrode material of supercapacitor mainly has carbon material, metal oxide and conducting polymer etc..
Carbon material be commonly used by people for earliest preparation supercapacitor electrode material, and at present industrialization it is most mature
Electrode material system has many advantages, such as that large specific surface area, conductive capability are strong, thermal stability is high, resistance to corrosion is strong, at low cost,
But the electrode specific capacitance of carbon material preparation is smaller, constrains development of the single carbon material in supercapacitor.
Metal oxide electrode material draws since its Faraday pseudo-capacitance is much larger than the electric double layer capacitance that carbon material generates
Extensive concern is played, but the electronics of metal oxide and the conductivity of ion are generally lower, the utilization rate of material is lower, high rate performance
Difference, the Cyclic voltamogram under higher scanning speed is bad, and higher cost.
It is based on the above characteristic of the two, carbon material is compound with metal oxide, it prepares with height ratio capacity and high circulation
The combination electrode material of stability realizes the reasonable balance between material property and cost.
Among metal oxide, RuO2And its hydrate is because have preferable conductivity and specific capacitance, and stable circulation,
As typical electrode material for super capacitor.Zheng (J.Power Sources, 62 (1996) 155-159) etc. is moved back in low temperature
Sol-gel method is used under the conditions of fire, obtained specific capacitance is up to the unformed RuO of 768F/g2·xH2O, and this material can be carried out
Complete redox reaction, greatly improves stock utilization.But because RuO2It is expensive and not friendly to environment
It is good, it is difficult to promote in practical applications, so need to find cheap metal oxide substitute.NiO,MnO2、Fe2O3、Co3O4
Deng, because its is cheap, better performances and become research hotspot.
Currently, the research compound with carbon material about metal oxide is largely unfolded.Banyan blueness (Acta
Electronica sinica, 2004,32 (8) 139-140) etc. in 1molL-1In KOH electrolyte, C/NiO compound electric is measured
Pole material specific capacitance is up to 263Fg-1.Lee (Nanoscale, 2012,4 (9): 2958-2961) etc. passes through hydro-thermal method for ɑ-
Fe2O3Nanotube is compound with graphene, prepares electrode material for super capacitor, and the material is under the current density of 3A/g, than electricity
Appearance reaches 181F/g.Li (Journal of physical Chemistry C, 118 (2014) 22865-22872) et al. will
MnO2Nanometer sheet is deposited on CNT surface and prepares CNT/MnO2Composite material, when current density is 1A/g, specific capacitance is
201F/g, when current density is 20A/g, specific capacitance 140F/g shows good high rate performance.Yan(China
Academic Journal Electronic Publishing House, X (2018) 04-0562-03) etc. utilize hydro-thermal legal system
Standby Co3O4/ N adulterates three-dimensional graphite (N-3DG) presoma, and Co is made after calcining3O4/ (N-3DG) composite material, in 6mol/L
In KOH electrolyte, when current density is 1A/g, specific capacitance 190F/g.
The pattern for the metal oxide materials that different preparation methods obtains is made a world of difference, and the electrochemistry of metal oxide
Performance is largely influenced by its crystal structure and microscopic appearance.Current various metal oxides and carbon material are compound
Preparation method fails simply and effectively to solve the problems, such as that metal oxide is easy to reunite.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The method that additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material carries out alkali-acid to bamboo charcoal first
The activation of two steps, then on the basis of hydro-thermal method, externally-applied magnetic field, impulse electric field, or apply pulse electric and magnetic field simultaneously, it makes
For the compound electrode material of metal oxide out and biomass carbon.This method raw material are cheap and easy to get, at low cost, simple and easy,
The metal oxide agglomeration of favorable reproducibility, additional electromagnetic field auxiliary preparation improves obvious, prepared combination electrode material
With very high specific capacity and cyclical stability.The method of the present invention simple process, it is easily controllable, reality, cost can be applied to
It is low.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of method that additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material, using bamboo charcoal
As raw material, bamboo charcoal is subjected to two step of alkali-acid and is activated, Activated Bamboo is obtained, then using metal salt, Activated Bamboo as water
Thermal response raw material, the Composite Field applied simultaneously using externally-applied magnetic field, impulse electric field or impulse electric field and magnetic field are carried out outfield and applied
The hydro-thermal reaction added obtains hydro-thermal reaction product；Then hydrothermal product is subjected to oxidation reaction, obtains metal oxide and biology
The compound material of matter charcoal, as electrode material.
As currently preferred technical solution, additional electromagnetic field auxiliary prepares metal oxide and biomass carbon compound electric
The method of pole material, its step are as follows:
A. bamboo charcoal and KOH are mixed in deionized water, stirred evenly as initial feed using bamboo charcoal, dried, moving back
High-temperature activation is carried out in stove, obtains the bamboo charcoal of alkali activation processing；As currently preferred technical solution, bamboo charcoal uses sub-micro
Meter level bamboo charcoal, when carrying out alkali activation processing, the mass ratio of bamboo charcoal and KOH are 1:1~1:4, and activation temperature is 500~900 DEG C, are risen
Warm rate is 3~10 DEG C/min, and soaking time is 1~4h；
B. dilute hydrochloric acid solution will be added by the bamboo charcoal that alkali is activated obtained in the step a, at room temperature into
Row magnetic agitation is uniform, bamboo charcoal is then washed to neutrality, then hydrofluoric acid solution is added into bamboo charcoal, and continue at room temperature
Magnetic agitation is uniform, then carries out processed bamboo charcoal to be washed to neutrality, filters, and obtains Activated Bamboo after drying, spare；
As currently preferred technical solution, the molar concentration of dilute hydrochloric acid solution is 0.5~3mol/L, hydrofluoric acid solution it is mole dense
Degree be 0.5~3mol/L, control the magnetic agitation time be 3~for 24 hours, drying temperature be 60~120 DEG C；
It c., will be soluble using soluble metallic salt, urea and the Activated Bamboo obtained in the step b as raw material
Metal salt and urea are dissolved in deionized water and obtain metal salt-urea mixed solution, are then added and live into metal salt-urea mixed solution
Change bamboo charcoal, and at room temperature, stirs the mixture for uniformly, obtaining bamboo charcoal-metal salt-urea mixed solution, as hydro-thermal reaction original
Feed liquid is spare；As currently preferred technical solution, the mass ratio of soluble metallic salt and bamboo charcoal is 1:1~1:10, is added
Urea quality be no less than the quality of soluble metallic salt；Using soluble metallic salt as raw material, preferably prepare containing Co2+、
Ni2+、Mn4+、Fe3+At least one of metal ion metal salt-urea mixed solution；
D. it will be poured into polytetrafluoroethyllining lining in bamboo charcoal-metal salt-urea mixed solution obtained in the step c,
Impulse electric field can be applied in hydrothermal reaction kettle outside liner, will applying pulse electric field liner be packed into reaction kettle after, place into
In high temperature furnace, and apply magnetic field in reaction kettle external enwergy；It is applied simultaneously using externally-applied magnetic field, impulse electric field or impulse electric field and magnetic field
The Composite Field added carries out the hydro-thermal reaction of outfield application to bamboo charcoal-metal salt-urea mixed solution, obtains hydro-thermal reaction product；Make
For currently preferred technical solution, the electric field strength of the applying pulse electric field is 0~100V/cm, magnetic field strength is 0~
200mT, the hydrothermal temperature be 80~160 DEG C, heating rate be 0.5~10 DEG C/min, soaking time be 6~for 24 hours；Into
The electric field strength of the preferred applying pulse electric field of one step is 0.5~5V/cm；Further preferred applied field strengths are 2~20mT；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven and dried, obtain dry hydro-thermal reaction product, it is spare；It is preferred that drying temperature
It is 60-120 DEG C；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, carries out oxygen in air
Change and keep the temperature, oxidation reaction processing is carried out to hydro-thermal reaction product, after the completion of oxidation reaction, furnace to be annealed is down to room temperature, takes
Oxidation product out；As currently preferred technical solution, controlling oxidizing temperature is 200~400 DEG C, and heating rate is 1~10
DEG C/min, soaking time is 30~360min；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in drying in oven, to finally obtain metal oxide and the compound electrode material of biomass carbon.It is preferred that
Drying temperature is 60-120 DEG C.
As currently preferred technical solution, composite wood is made in prepared metal oxide-bamboo charcoal composite material
Expect electrode, the specific capacitance in the case where current density is 1A/g is not less than 301F/g.The metal oxidation that above-mentioned preparation method obtains
Object/bamboo charcoal composite material is applied to supercapacitor as electrode material.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. bamboo charcoal of the method for the present invention by the activation of two step of alkali-acid has high-specific surface area, to the specific capacity of electrode material
Promotion have very great help；Due to biomass carbon because of its abundance and renewable, especially bamboo because having natural porous
Structure, the bamboo charcoal of preparation macropore rich in, mesoporous and micropore, so, in the electrode material of all carbon materials preparation, bamboo
The electrode material overall performance of charcoal preparation is more outstanding, and bamboo charcoal gap abundant can provide life appropriate for metal oxide
Long position, so that the combination that the two is closer, the present invention utilizes the material property of this cost advantage and bamboo charcoal, aoxidizes with metal
Object, which combines, prepares biological carbon composite, and has given full play to metal oxide-bamboo charcoal composite material electric conductivity, intensity and light
The advantage of quantization；
2. the method for the present invention prepares metal oxide and biomass carbon combination electrode material using additional electromagnetic field auxiliary, can
Effectively to change metal oxide crystal structure and microscopic appearance, improve metal oxide it is easy to reunite the case where, be conducive to mention
The chemical property of high combination electrode material；
3. the metal oxide crystal that the method for the present invention is prepared under additional electromagnetic field auxiliary is easily along the direction of electromagnetic wire
Forming core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile electromagnetic field is equivalent to an energy field, passes through
Vibration limits make forming core particle become smaller, and crystal growth rate is made to change, this is all conducive to improve metal oxide microparticle
Agglomeration, be also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improve the ratio of the combination electrode material
Capacitor and cyclical stability；
4. magnetic metal oxide prepared by the present invention/bamboo charcoal combination electrode material, compared to preparation when being not powered on magnetic field
Such combination electrode material, under identical current density, specific capacitance obtains promotion by a relatively large margin.
Detailed description of the invention
Fig. 1 is the hydro-thermal reaction principle of device schematic diagram for the additional electromagnetic field auxiliary that one method of the embodiment of the present invention uses.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail is described further above scheme, this hair
Details are as follows for bright preferred embodiment:
Embodiment one
In the present embodiment, referring to Fig. 1, a kind of additional electromagnetic field auxiliary prepares metal oxide and biomass carbon compound electric
The method of pole material, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 12g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 700 DEG C with the heating rate of 5 DEG C/min, heat preservation 3h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal uses
Submicron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 2mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 12 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 2mol/L, and continues magnetic agitation at room temperature 12 hours, then will process
Bamboo charcoal carry out being washed to neutrality, filter, obtain Activated Bamboo after being placed in baking oven 80 DEG C of drying, it is spare；The present embodiment pair
Bamboo charcoal carries out acid activation processing, and the bamboo charcoal by the activation of two step of alkali-acid is with high-specific surface area, to the specific capacity of electrode material
Promotion has very great help；
C. Co (the NO of 0.145g is used3)2·6H2O, the work obtained in the step b of the urea of 0.145g and 0.2g
Change bamboo charcoal as raw material, by Co (NO3)2·6H2O and urea are dissolved in deionized water and obtain containing Co2+Urea mixed solution, then
To containing Co2+Urea mixed solution in Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Co2+
Bamboo charcoal-urea mixed solution, it is spare as hydro-thermal presoma turbid solution；
D. it will contain Co obtained in the step c2+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
Apply the impulse electric field that electric field strength is 1V/cm in liner, in the hydrothermal reaction kettle outside liner, it will be in applying pulse electric field
It after lining is packed into reaction kettle, places into high temperature furnace, and applies the magnetic field that magnetic field strength is 5mT in reaction kettle external enwergy；Using pulse
The Composite Field that electric field and magnetic field apply simultaneously rises to 100 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 12h, to containing Co2+Bamboo
Charcoal-urea mixed solution carries out the hydro-thermal reaction of outfield application, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 5 DEG C/min rises to 300 DEG C, keeps the temperature 120min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The metal oxide crystal that the present embodiment method is prepared under additional electromagnetic field auxiliary is easily along the direction of electromagnetic wire
Forming core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile electromagnetic field is equivalent to an energy field, passes through
Vibration limits make forming core particle become smaller, and crystal growth rate is made to change, this is all conducive to improve metal oxide microparticle
Agglomeration, be also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improve the ratio of the combination electrode material
Capacitor and cyclical stability；Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to being not powered on magnetic
Such combination electrode material prepared when field, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table
1。
Embodiment two
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, a kind of additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material
Method, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 12g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 700 DEG C with the heating rate of 5 DEG C/min, heat preservation 3h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal uses
Submicron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 2mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 12 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 2mol/L, and continues magnetic agitation at room temperature 12 hours, then will process
Bamboo charcoal carry out being washed to neutrality, filter, obtain Activated Bamboo after being placed in baking oven 80 DEG C of drying, it is spare；The present embodiment pair
Bamboo charcoal carries out acid activation processing, and the bamboo charcoal by the activation of two step of alkali-acid is with high-specific surface area, to the specific capacity of electrode material
Promotion has very great help；
C. Ni (the NO of 0.145g is used3)2·6H2O, the work obtained in the step b of the urea of 0.145g and 0.2g
Change bamboo charcoal as raw material, by Ni (NO3)2·6H2O and urea are dissolved in deionized water and obtain containing Ni2+Urea mixed solution, then
To containing Ni2+Urea mixed solution in Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Ni2+
Bamboo charcoal-urea mixed solution, it is spare as hydro-thermal presoma turbid solution；
D. it will contain Ni obtained in the step c2+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
Apply the impulse electric field that electric field strength is 1V/cm in liner, in the hydrothermal reaction kettle outside liner, it will be in applying pulse electric field
It after lining is packed into reaction kettle, places into high temperature furnace, and applies the magnetic field that magnetic field strength is 5mT in reaction kettle external enwergy；Using pulse
The Composite Field that electric field and magnetic field apply simultaneously rises to 100 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 12h, to containing Ni2+Bamboo
Charcoal-urea mixed solution carries out the hydro-thermal reaction of outfield application, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 5 DEG C/min rises to 300 DEG C, keeps the temperature 120min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The metal oxide crystal that the present embodiment method is prepared under additional electromagnetic field auxiliary is easily along the direction of electromagnetic wire
Forming core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile electromagnetic field is equivalent to an energy field, passes through
Vibration limits make forming core particle become smaller, and crystal growth rate is made to change, this is all conducive to improve metal oxide microparticle
Agglomeration, be also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improve the ratio of the combination electrode material
Capacitor and cyclical stability；Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to being not powered on magnetic
Such combination electrode material prepared when field, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table
1。
Embodiment three
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material
Method, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 12g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 700 DEG C with the heating rate of 5 DEG C/min, heat preservation 3h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal uses
Submicron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 2mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 12 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 2mol/L, and continues magnetic agitation at room temperature 12 hours, then will process
Bamboo charcoal carry out being washed to neutrality, filter, obtain Activated Bamboo after being placed in baking oven 80 DEG C of drying, it is spare；The present embodiment pair
Bamboo charcoal carries out acid activation processing, and the bamboo charcoal by the activation of two step of alkali-acid is with high-specific surface area, to the specific capacity of electrode material
Promotion has very great help；
C. the FeCl of 0.135g is used3·6H2O, the activation obtained in the step b of the urea of 0.135g and 0.2g
Bamboo charcoal is as raw material, by FeCl3·6H2O and urea are dissolved in deionized water and obtain containing Fe3+Urea mixed solution, then to containing
There is Fe3+Urea mixed solution in Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Fe3+Bamboo
Charcoal-urea mixed solution, it is spare as hydro-thermal presoma turbid solution；
D. it will contain Fe obtained in the step c3+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
Apply the impulse electric field that electric field strength is 1V/cm in liner, in the hydrothermal reaction kettle outside liner, it will be in applying pulse electric field
It after lining is packed into reaction kettle, places into high temperature furnace, and applies the magnetic field that magnetic field strength is 5mT in reaction kettle external enwergy；Using pulse
The Composite Field that electric field and magnetic field apply simultaneously rises to 100 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 12h, to containing Fe3+Bamboo
Charcoal-urea mixed solution carries out the hydro-thermal reaction of outfield application, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 5 DEG C/min rises to 300 DEG C, keeps the temperature 120min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The metal oxide crystal that the present embodiment method is prepared under additional electromagnetic field auxiliary is easily along the direction of electromagnetic wire
Forming core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile electromagnetic field is equivalent to an energy field, passes through
Vibration limits make forming core particle become smaller, and crystal growth rate is made to change, this is all conducive to improve metal oxide microparticle
Agglomeration, be also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improve the ratio of the combination electrode material
Capacitor and cyclical stability；Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to being not powered on magnetic
Such combination electrode material prepared when field, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table
1。
Example IV
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material
Method, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 12g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 700 DEG C with the heating rate of 5 DEG C/min, heat preservation 3h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal uses
Submicron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 2mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 12 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 2mol/L, and continues magnetic agitation at room temperature 12 hours, then will process
Bamboo charcoal carry out being washed to neutrality, filter, obtain Activated Bamboo after being placed in baking oven 80 DEG C of drying, it is spare；The present embodiment pair
Bamboo charcoal carries out acid activation processing, and the bamboo charcoal by the activation of two step of alkali-acid is with high-specific surface area, to the specific capacity of electrode material
Promotion has very great help；
C. the MnF of 0.065g is used4, 0.065g urea and 0.2g the Activated Bamboo obtained in the step b make
For raw material, by MnF4Deionized water is dissolved in urea to obtain containing Mn4+Urea mixed solution, then to containing Mn4+Urea it is mixed
It closes in liquid and Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Mn4+Bamboo charcoal-urea mixed solution,
It is spare as hydro-thermal presoma turbid solution；
D. it will contain Mn obtained in the step c4+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
Apply the impulse electric field that electric field strength is 1V/cm in liner, in the hydrothermal reaction kettle outside liner, it will be in applying pulse electric field
It after lining is packed into reaction kettle, places into high temperature furnace, and applies the magnetic field that magnetic field strength is 5mT in reaction kettle external enwergy；Using pulse
The Composite Field that electric field and magnetic field apply simultaneously rises to 100 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 12h, to containing Mn4+Bamboo
Charcoal-urea mixed solution carries out the hydro-thermal reaction of outfield application, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 5 DEG C/min rises to 300 DEG C, keeps the temperature 120min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The metal oxide crystal that the present embodiment method is prepared under additional electromagnetic field auxiliary is easily along the direction of electromagnetic wire
Forming core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile electromagnetic field is equivalent to an energy field, passes through
Vibration limits make forming core particle become smaller, and crystal growth rate is made to change, this is all conducive to improve metal oxide microparticle
Agglomeration, be also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improve the ratio of the combination electrode material
Capacitor and cyclical stability；Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to being not powered on magnetic
Such combination electrode material prepared when field, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table
1。
Embodiment five
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material
Method, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 16g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 500 DEG C with the heating rate of 3 DEG C/min, heat preservation 4h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal uses
Submicron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 0.5mol/ by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
The dilute hydrochloric acid solution of L carries out magnetic agitation 12 hours at room temperature, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 0.5mol/L, and continues magnetic agitation at room temperature 12 hours, then will processing
The bamboo charcoal crossed carries out being washed to neutrality, filters, and is placed in baking oven the Activated Bamboo that obtains after 120 DEG C of drying, spare；The present embodiment
Acid activation processing is carried out to bamboo charcoal, the bamboo charcoal by the activation of two step of alkali-acid has high-specific surface area, to the specific capacity of electrode material
Promotion have very great help；
C. the MnF of 0.065g is used4, 0.065g urea and 0.2g the Activated Bamboo obtained in the step b make
For raw material, by MnF4Deionized water is dissolved in urea to obtain containing Mn4+Urea mixed solution, then to containing Mn4+Urea it is mixed
It closes in liquid and Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Mn4+Bamboo charcoal-urea mixed solution,
It is spare as hydro-thermal presoma turbid solution；
D. it will contain Mn obtained in the step c4+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
Apply the impulse electric field that electric field strength is 5V/cm in liner, in the hydrothermal reaction kettle outside liner, it will be in applying pulse electric field
It after lining is packed into reaction kettle, places into high temperature furnace, and applies the magnetic field that magnetic field strength is 20mT in reaction kettle external enwergy；Using pulse
The Composite Field that electric field and magnetic field apply simultaneously rises to 80 DEG C with the heating rate of 0.5 DEG C/min, heat preservation for 24 hours, to containing Mn4+'s
Bamboo charcoal-urea mixed solution carries out the hydro-thermal reaction of outfield application, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 10 DEG C/min rises to 400 DEG C, keeps the temperature 30min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The metal oxide crystal that the present embodiment method is prepared under additional electromagnetic field auxiliary is easily along the direction of electromagnetic wire
Forming core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile electromagnetic field is equivalent to an energy field, passes through
Vibration limits make forming core particle become smaller, and crystal growth rate is made to change, this is all conducive to improve metal oxide microparticle
Agglomeration, be also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improve the ratio of the combination electrode material
Capacitor and cyclical stability；Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to being not powered on magnetic
Such combination electrode material prepared when field, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table
1。
Embodiment six
The present embodiment is substantially the same as in the previous example, and is particular in that:
In the present embodiment, a kind of additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material
Method, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 4g is mixed in 50ml deionized water as initial feed using bamboo charcoal, stirring is equal
It is even, 80 DEG C of drying in baking oven are placed in, then in the lehr, rise to 900 DEG C with the heating rate of 10 DEG C/min, heat preservation 1h is carried out
High-temperature alkali activation, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal is using sub-
Micron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 3mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 1.5 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 3mol/L, and continues magnetic agitation at room temperature 1.5 hours, then will processing
The bamboo charcoal crossed carries out being washed to neutrality, filters, and is placed in baking oven the Activated Bamboo that obtains after 60 DEG C of drying, spare；The present embodiment
Acid activation processing is carried out to bamboo charcoal, the bamboo charcoal by the activation of two step of alkali-acid has high-specific surface area, to the specific capacity of electrode material
Promotion have very great help；
C. the MnF of 0.065g is used4, 0.065g urea and 0.2g the Activated Bamboo obtained in the step b make
For raw material, by MnF4Deionized water is dissolved in urea to obtain containing Mn4+Urea mixed solution, then to containing Mn4+Urea it is mixed
It closes in liquid and Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Mn4+Bamboo charcoal-urea mixed solution,
It is spare as hydro-thermal presoma turbid solution；
D. it will contain Mn obtained in the step c4+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
Apply the impulse electric field that electric field strength is 0.5V/cm in liner, in the hydrothermal reaction kettle outside liner, by applying pulse electric field
It after liner is packed into reaction kettle, places into high temperature furnace, and applies the magnetic field that magnetic field strength is 2mT in reaction kettle external enwergy；Using arteries and veins
It rushes electric field and Composite Field that magnetic field applies simultaneously, rises to 160 DEG C with the heating rate of 10 DEG C/min, keep the temperature 6h, to containing Mn4+'s
Bamboo charcoal-urea mixed solution carries out the hydro-thermal reaction of outfield application, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 1 DEG C/min rises to 200 DEG C, keeps the temperature 360min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The metal oxide crystal that the present embodiment method is prepared under additional electromagnetic field auxiliary is easily along the direction of electromagnetic wire
Forming core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile electromagnetic field is equivalent to an energy field, passes through
Vibration limits make forming core particle become smaller, and crystal growth rate is made to change, this is all conducive to improve metal oxide microparticle
Agglomeration, be also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improve the ratio of the combination electrode material
Capacitor and cyclical stability；Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to being not powered on magnetic
Such combination electrode material prepared when field, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table
1。
Embodiment seven
In the present embodiment, a kind of extra electric field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material
Method, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 12g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 700 DEG C with the heating rate of 5 DEG C/min, heat preservation 3h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal uses
Submicron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 2mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 12 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 2mol/L, and continues magnetic agitation at room temperature 12 hours, then will process
Bamboo charcoal carry out being washed to neutrality, filter, obtain Activated Bamboo after being placed in baking oven 80 DEG C of drying, it is spare；The present embodiment pair
Bamboo charcoal carries out acid activation processing, and the bamboo charcoal by the activation of two step of alkali-acid is with high-specific surface area, to the specific capacity of electrode material
Promotion has very great help；
C. Co (the NO of 0.145g is used3)2·6H2O, the work obtained in the step b of the urea of 0.145g and 0.2g
Change bamboo charcoal as raw material, by Co (NO3)2·6H2O and urea are dissolved in deionized water and obtain containing Co2+Urea mixed solution, then
To containing Co2+Urea mixed solution in Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Co2+
Bamboo charcoal-urea mixed solution, it is spare as hydro-thermal presoma turbid solution；
D. it will contain Co obtained in the step c2+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
Apply the impulse electric field that electric field strength is 1V/cm in liner, in the hydrothermal reaction kettle outside liner, it will be in applying pulse electric field
After lining is packed into reaction kettle, place into high temperature furnace；Using impulse electric field, 100 DEG C are risen to the heating rate of 5 DEG C/min, heat preservation
12h, to containing Co2+Bamboo charcoal-urea mixed solution carry out electric field application hydro-thermal reaction, obtain hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 5 DEG C/min rises to 300 DEG C, keeps the temperature 120min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The present embodiment method prepares metal oxide and the compound electrode material of biomass carbon under extra electric field auxiliary, obtains
The metal oxide nano-wire arrangement arrived is more regular；Meanwhile electric field is equivalent to an energy field, makes forming core by vibration limits
Particle becomes smaller, and crystal growth rate is made to change, this is all conducive to the agglomeration for improving metal oxide microparticle, also favorably
It is preferably combined between metal oxide and bamboo charcoal, and then improves the specific capacitance and cyclical stability of the combination electrode material；
Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to prepared when being not powered on such is compound
Electrode material, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table 1.
Embodiment eight
In the present embodiment, a kind of externally-applied magnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material
Method, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 12g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 700 DEG C with the heating rate of 5 DEG C/min, heat preservation 3h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；The present embodiment bamboo charcoal uses
Submicron order bamboo charcoal carries out alkali activation processing, the preliminary specific surface area for promoting bamboo charcoal to bamboo charcoal；
It b. is 2mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 12 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 2mol/L, and continues magnetic agitation at room temperature 12 hours, then will process
Bamboo charcoal carry out being washed to neutrality, filter, obtain Activated Bamboo after being placed in baking oven 80 DEG C of drying, it is spare；The present embodiment pair
Bamboo charcoal carries out acid activation processing, and the bamboo charcoal by the activation of two step of alkali-acid is with high-specific surface area, to the specific capacity of electrode material
Promotion has very great help；
C. Co (the NO of 0.145g is used3)2·6H2O, the work obtained in the step b of the urea of 0.145g and 0.2g
Change bamboo charcoal as raw material, by Co (NO3)2·6H2O and urea are dissolved in deionized water and obtain containing Co2+Urea mixed solution, then
To containing Co2+Urea mixed solution in Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Co2+
Bamboo charcoal-urea mixed solution, it is spare as hydro-thermal presoma turbid solution；
D. it will contain Co obtained in the step c2+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
It in liner, after liner is packed into reaction kettle, places into high temperature furnace, and applies the magnetic that magnetic field strength is 5mT in reaction kettle external enwergy
?；Applied using magnetic field, rise to 100 DEG C with the heating rate of 5 DEG C/min, keep the temperature 12h, to containing Co2+Bamboo charcoal-urea mixing
Liquid carries out the hydro-thermal reaction of magnetic field application, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 5 DEG C/min rises to 300 DEG C, keeps the temperature 120min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；The hydrothermal product that embodiment is obtained is placed in the lehr,
It quickly aoxidizes and keeps the temperature in air, obtain product after the completion of oxidation, technique is easily controllable；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound electrode of biomass carbon
Material.
The metal oxide crystal that the present embodiment method is prepared under externally-applied magnetic field auxiliary is easily along the direction shape of the magnetic line of force
Core and growth, obtained metal oxide nano-wire arrangement are more regular；Meanwhile magnetic field is equivalent to an energy field, passes through vibration
It destroys so that forming core particle becomes smaller, crystal growth rate is made to change, this is all conducive to the group for improving metal oxide microparticle
Poly- phenomenon is also beneficial to preferably be combined between metal oxide and bamboo charcoal, and then improves the specific capacitance of the combination electrode material
And cyclical stability；Magnetic metal oxide manufactured in the present embodiment/bamboo charcoal combination electrode material, compared to not plus magnetic field when system
Such standby combination electrode material, under identical current density, specific capacitance obtains promotion by a relatively large margin, participates in table 1.
Comparative example:
In this comparative example, a method of metal oxide and biomass carbon composite material being prepared, its step are as follows:
A. the KOH of the bamboo charcoal of 4g and 12g is mixed in 50ml deionized water as initial feed using bamboo charcoal, is stirred
Uniformly, 80 DEG C of drying are placed in baking oven, then in the lehr, rise to 700 DEG C with the heating rate of 5 DEG C/min, heat preservation 3h into
The activation of row high-temperature alkali, furnace to be annealed are down to room temperature, take out product, obtain the bamboo charcoal of alkali activation processing；
It b. is 2mol/L by 200ml molar concentration is added by the bamboo charcoal that alkali is activated obtained in the step a
Dilute hydrochloric acid solution, at room temperature carry out magnetic agitation 12 hours, bamboo charcoal is then washed to neutrality, then be added into bamboo charcoal
200ml molar concentration is the hydrofluoric acid solution of 2mol/L, and continues magnetic agitation at room temperature 12 hours, then will process
Bamboo charcoal carry out being washed to neutrality, filter, obtain Activated Bamboo after being placed in baking oven 80 DEG C of drying, it is spare；
C. Co (the NO of 0.145g is used3)2·6H2O, the work obtained in the step b of the urea of 0.145g and 0.2g
Change bamboo charcoal as raw material, by Co (NO3)2·6H2O and urea are dissolved in deionized water and obtain containing Co2+Urea mixed solution, then
To containing Co2+Urea mixed solution in Activated Bamboo is added, and at room temperature, stir the mixture for uniformly, obtaining containing Co2+
Bamboo charcoal-urea mixed solution, it is spare as hydro-thermal presoma turbid solution；
D. it will contain Co obtained in the step c2+Bamboo charcoal-urea mixed solution pour into the polytetrafluoroethylene (PTFE) of 100ml
In reaction kettle, then reaction kettle is put into high temperature furnace, rises to 100 DEG C with the heating rate of 5 DEG C/min, keep the temperature 12h, to containing
Co2+Bamboo charcoal-urea mixed solution carry out hydro-thermal reaction, obtain hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, will obtain
Clean hydro-thermal reaction product be placed in baking oven carry out dry 4h at 80 DEG C, obtain dry hydro-thermal reaction product, it is spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, in air atmosphere, with
The heating rate of 5 DEG C/min rises to 300 DEG C, keeps the temperature 120min, carries out oxidation reaction processing to hydro-thermal reaction product, anti-in oxidation
After the completion of answering, furnace to be annealed is down to room temperature, takes out oxidation product；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, it is clean by what is obtained
Net oxidation product is placed in baking oven and dries 4h at 80 DEG C, to finally obtain metal oxide and the compound material of biomass carbon
Material.
The present embodiment is that metal oxide and the compound material of biomass carbon are prepared in the case where being not powered on magnetic field condition, participates in table
1。
The analysis of the electrochemical property test of the above embodiment of the present invention and comparative example:
Electrode material, acetylene black and the ptfe emulsion respectively prepared by each embodiment and comparative example is with mass ratio
It is uniformly mixed for the ratio of 8:1:1, electrode is made.
Using the compound electric pole piece of above-mentioned preparation as working electrode, platinized platinum is used as to electrode, and saturated calomel electrode (SCE) is made
For reference electrode, electrolyte is the KOH solution of 3mol/L, three electrode test systems is formed, in electrochemical workstation CHI660E instrument
Device carries out electrochemical property test.Each electrode of the above embodiment of the present invention and comparative example is measured under the current density of 1A/g
Specific capacity result it is as shown in the table:
As shown in Table 1, embodiment seven and implementation eight compare comparative example, in 1A/g only with electric field or only with magnetic field
Current density under the electrode specific capacitance that measures improve 28.1% or more than comparative example electrode.Embodiment five and implementation six change
Parameter other than hydro-thermal reaction, compares comparative example, and the electrode specific capacitance measured under the current density of 1A/g is still higher than comparative example
Electrode.The Composite Field that embodiment one, two, three and four is applied simultaneously using impulse electric field and magnetic field, under the current density of 1A/g
The electrode specific capacitance measured improves the electricity of the material preparation of 43.83% or more or even the preparation of embodiment one than comparative example electrode
The electrode specific capacitance that pole measures under the current density of 1A/g improves 72.77% than comparative example electrode.Therefore, the present invention is above-mentioned
The method that embodiment additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material, first to submicron order bamboo
Charcoal carries out the activation of two step of alkali-acid, then using bamboo charcoal, metal salt and urea as raw material, successively passes through outer power-up, the hydro-thermal reaction in magnetic field
With oxidation step in air, the combination electrode material with height ratio capacity and high circulation stability is prepared.This method is super
The fields such as the preparation of capacitor electrode material have a extensive future.
Combination attached drawing of the embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
The skill of the method for metal oxide and biomass carbon combination electrode material is prepared without departing from additional electromagnetic field auxiliary of the present invention
Art principle and inventive concept, belong to protection scope of the present invention.
Claims (10)
1. a kind of method that additional electromagnetic field auxiliary prepares metal oxide and biomass carbon combination electrode material, feature exist
In: using bamboo charcoal as raw material, bamboo charcoal is subjected to two step of alkali-acid and is activated, Activated Bamboo is obtained, then by metal salt, work
Change bamboo charcoal as hydro-thermal reaction raw material, is applied simultaneously using externally-applied magnetic field, impulse electric field or impulse electric field with magnetic field compound
, the hydro-thermal reaction of outfield application is carried out, hydro-thermal reaction product is obtained；Then hydrothermal product is subjected to oxidation reaction, obtains gold
Belong to oxide and the compound material of biomass carbon, as electrode material.
2. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 1
Method, which is characterized in that its step are as follows:
A. bamboo charcoal and KOH are mixed in deionized water, stirred evenly as initial feed using bamboo charcoal, dried, in annealing furnace
Middle carry out high-temperature activation obtains the bamboo charcoal of alkali activation processing；
B. dilute hydrochloric acid solution will be added by the bamboo charcoal that alkali is activated obtained in the step a, carries out magnetic at room temperature
Power stirs evenly, and bamboo charcoal is then washed to neutrality, then hydrofluoric acid solution is added into bamboo charcoal, and continue magnetic force at room temperature
It stirs evenly, then carries out processed bamboo charcoal to be washed to neutrality, filter, obtain Activated Bamboo after drying, it is spare；
C. using soluble metallic salt, urea and the Activated Bamboo obtained in the step b as raw material, by soluble metal
Salt and urea are dissolved in deionized water and obtain metal salt-urea mixed solution, and activation bamboo is then added into metal salt-urea mixed solution
Charcoal, and at room temperature, it stirs the mixture for uniformly, bamboo charcoal-metal salt-urea mixed solution being obtained, as hydro-thermal reaction material liquid
It is spare；
D. it will be poured into polytetrafluoroethyllining lining in bamboo charcoal-metal salt-urea mixed solution obtained in the step c, in liner
Impulse electric field can be applied in outer hydrothermal reaction kettle, will applying pulse electric field liner be packed into reaction kettle after, place into high temperature
In furnace, and apply magnetic field in reaction kettle external enwergy；Applied simultaneously using externally-applied magnetic field, impulse electric field or impulse electric field and magnetic field
Composite Field carries out the hydro-thermal reaction of outfield application to bamboo charcoal-metal salt-urea mixed solution, obtains hydro-thermal reaction product；
E. will the hydro-thermal reaction product obtained in the step d cleaned with deionized water after filter again, it is clean by what is obtained
Water purification thermal response product, which is placed in baking oven, is dried, and dry hydro-thermal reaction product is obtained, spare；
F. hydro-thermal reaction product of the step e described in the step after dry is placed in the lehr, is aoxidized in air simultaneously
Heat preservation carries out oxidation reaction processing to hydro-thermal reaction product, and after the completion of oxidation reaction, furnace to be annealed is down to room temperature, takes out oxygen
Change product；
G. it is filtered again after the oxidation product prepared in the step f being cleaned with deionized water, the clean oxygen that will be obtained
Change product and be placed in drying in oven, to finally obtain metal oxide and the compound electrode material of biomass carbon.
3. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 2
Method, it is characterised in that: in the step a, bamboo charcoal uses submicron order bamboo charcoal, when carrying out alkali activation processing, bamboo charcoal and KOH's
Mass ratio is 1:1~1:4, and activation temperature is 500~900 DEG C, and heating rate is 3~10 DEG C/min, and soaking time is 1~4h.
4. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 2
Method, it is characterised in that: in the step b, the molar concentration of dilute hydrochloric acid solution is 0.5~3mol/L, and hydrofluoric acid solution rubs
Your concentration is 0.5~3mol/L, the control magnetic agitation time is 3~for 24 hours, drying temperature is 60~120 DEG C.
5. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 2
Method, it is characterised in that: in the step c, the mass ratio of soluble metallic salt and bamboo charcoal is 1:1~1:10, the urea of addition
Quality is no less than the quality of soluble metallic salt.
6. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 2
Method, it is characterised in that: in the step c, using soluble metallic salt as raw material, preparation contains Co2+、Ni2+、Mn4+、Fe3+
At least one of metal ion metal salt-urea mixed solution.
7. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 2
Method, it is characterised in that: in the step d, the electric field strength of the applying pulse electric field is 0~100V/cm, and magnetic field strength is
0~200mT, the hydrothermal temperature be 80~160 DEG C, heating rate be 0.5~10 DEG C/min, soaking time be 6~
24h。
8. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 7
Method, it is characterised in that: in the step d, the electric field strength of applying pulse electric field is 0.5~5V/cm；Applied field strengths are
2~20mT.
9. additional electromagnetic field auxiliary prepares the side of metal oxide and biomass carbon combination electrode material according to claim 2
Method, it is characterised in that: in the step f, control oxidizing temperature is 200~400 DEG C, and heating rate is 1~10 DEG C/min, is protected
The warm time is 30~360min.
10. additional electromagnetic field auxiliary described according to claim 1~any one of 9 prepares metal oxide and biomass carbon is multiple
The method of composite electrode material, it is characterised in that: composite material electricity is made in prepared metal oxide-bamboo charcoal composite material
Pole, the specific capacitance in the case where current density is 1A/g are not less than 301F/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910046382.4A CN109830376B (en) | 2019-01-18 | 2019-01-18 | Method for preparing metal oxide and biomass charcoal composite electrode material with assistance of external electromagnetic field |
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Cited By (3)
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| CN110749634A (en) * | 2019-10-21 | 2020-02-04 | 遵义师范学院 | NiO/BC composite material and preparation method thereof |
| CN110749633A (en) * | 2019-10-21 | 2020-02-04 | 遵义师范学院 | Method for modifying electrode by NiO/BC composite material and application thereof |
| CN112010359A (en) * | 2020-07-09 | 2020-12-01 | 江苏大学 | NiO/C nano composite electrode material and preparation method and application thereof |
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| CN110749633A (en) * | 2019-10-21 | 2020-02-04 | 遵义师范学院 | Method for modifying electrode by NiO/BC composite material and application thereof |
| CN112010359A (en) * | 2020-07-09 | 2020-12-01 | 江苏大学 | NiO/C nano composite electrode material and preparation method and application thereof |
| CN112010359B (en) * | 2020-07-09 | 2024-02-13 | 江苏大学 | NiO/C nano composite electrode material and preparation method and application thereof |
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