CN107010624B - A kind of nitrogen for electrode of super capacitor, boron doping porous charcoal and preparation method thereof - Google Patents
A kind of nitrogen for electrode of super capacitor, boron doping porous charcoal and preparation method thereof Download PDFInfo
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- CN107010624B CN107010624B CN201710269708.0A CN201710269708A CN107010624B CN 107010624 B CN107010624 B CN 107010624B CN 201710269708 A CN201710269708 A CN 201710269708A CN 107010624 B CN107010624 B CN 107010624B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The nitrogen that the invention discloses a kind of for electrode of super capacitor, boron doping porous charcoal and preparation method thereof, belong to energy and material and applied technical field.The present invention, respectively using nitrogenous fertilizer and boron fertilizer as nitrogen source and boron source, is made through carbonization-activation technique using natural reed bar as carbon source.Nitrogen obtained by the present invention, boron doping porous charcoal have both the classification three dimensional pore structures of micropore and mesoporous, and aperture is mainly distributed on 1~5 nanometer, and specific surface area is 1400~1700 meters squared per grams, and nitrating atomic ratio is 6~8%, and boron-doping atomic ratio is 2~4%.When as electrode material for super capacitor, its 1 peace/gram current density under with 225~250 faraday/gram specific capacitance, after recycling 5000 charge and discharge, capacitor retain be higher than 95%, under the power density of 500 watts/kilogram with 30~35 watt-hours/kilogram energy density.
Description
Technical field
The invention belongs to energy and material and applied technical fields, and in particular to a kind of nitrogen for electrode of super capacitor,
Boron doping porous charcoal and preparation method thereof.
Background technique
Porous charcoal due to large specific surface area, pore structure is adjustable, chemical stability is good and the advantages such as at low cost at
For the preferred electrode material of supercapacitor.Porous carbon electrode is mainly formed at electrode/electrolyte interface in supercapacitor
Electric double layer stores energy, and therefore, the absorbent charcoal material of high-efficiency energy-storage should have the bigger serface conducive to charge accumulated
With the pore structure convenient for electrolyte wetting and ion fast transferring.The study found that the porous charcoal of Heteroatom doping is more traditional more
Hole charcoal has more excellent chemical property.
Raw material used by preparation porous charcoal be it is various, small organic molecule, polymer, petroleum coke, natural products etc. are equal
It can be used as carbon source.
Such as application No. is 201310297709.8 patent disclose it is a kind of using complex salicylate prepare it is super
The method of capacitor porous charcoal, porous charcoal obtained have the specific surface area of up to 2000 meters squared per grams, and capacitive property is good
It is good, but cost of material is high, preparation process is cumbersome, and structure is not easy to control, it is difficult to obtain scale application.
Such as application No. is 201410508582.4 patents to disclose a kind of preparation method of porous carbon material, specifically relates to
And a kind of method that the Heat-resistant polymer film leftover pieces using difficult reclaiming prepare porous carbon electrode material, although using
Cheap thin polymer film leftover pieces are carbon source, and porous charcoal specific surface area obtained is 1000~2000 meters squared per grams, but is led
Electrically it is bad, specific capacitance only have 160~180 faraday/gram, be unfavorable for commercialization answer.
Such as application No. is 201410506124.7 patents to disclose a kind of preparation method of super capacitor porous charcoal,
It uses petroleum coke, acrylic resin etc. for raw material, porous charcoal is made after high-temperature activation, specific surface area is 1700~1900 flat
Square rice/gram, but specific capacitance be 120~190 faraday/gram, still in low-level, limit the extensive use of porous charcoal.
Such as document Chen H, Xiong Y, Yu T, et al.Boron and nitrogen co-doped porous
carbon with a high concentration of boron and its superior capacitive
Behavior [J] .Carbon, 2017,113:266-273. report a kind of using phenol and formaldehyde as raw material, melamine and boron
Acid is nitrogen source and boron source, then using silica as template, is prepared for having the nitrogen of hierarchical structure, boron total after multi step strategy technique
The porous charcoal of doping, although with 189~304 faraday/gram specific capacitance, its specific surface area is lower, only 648 squares
Rice/gram, and the virose chemical reagent such as the phenol used and formaldehyde, it easily pollutes the environment, does not meet clean energy resource
Development trend.
In numerous raw materials that can be used as preparation porous charcoal, the advantages that natural products is widely distributed, cheap and easy to get because of its
And it is come by extensive popularization.
Such as the side that super porous Carbon Materials are prepared with persimmon pericarp is disclosed application No. is 201510611801.6 patent
Method uses persimmon pericarp for raw material, porous charcoal is made after being carbonized, being activated, specific surface area is 1186 meters squared per grams, but the material
The electro-chemical activity of material is low, is not suitable for as electrode material for super capacitor.
Summary of the invention
The object of the present invention is to provide a kind of can be applied to electrode material for super capacitor, the light, specific surfaces with quality
Accumulate the nitrogen that big, hole is classified and electro-chemical activity is high, boron doping porous charcoal and preparation method thereof.
A kind of nitrogen for electrode of super capacitor provided by the invention, boron doping porous charcoal, are with natural reed bar
It is made through carbonization-activation technique, which has both micropore for raw material respectively using nitrogenous fertilizer and boron fertilizer as nitrogen source and boron source
With the classification three dimensional pore structures of mesoporous, specific surface area is 1400~1700 meters squared per grams, and nitrating atomic ratio is 6~8%, is mixed
Boron atom ratio is 2~4%.It has the pore structure of classification, and aperture is mainly distributed on 1~5 nanometer.As super capacitor electrode
When the material of pole, 1 peace/gram current density under with 225~250 faraday/gram specific capacitance, recycle 5000 charge and discharge
Afterwards, capacitor retain be higher than 95%, under the power density of 500 watts/kilogram with 30~35 watt-hours/kilogram energy density.
A kind of preparation method of the nitrogen, boron doping porous charcoal that the present invention provides above-mentioned for electrode of super capacitor,
Include the following steps:
(1) using natural reed bar as raw material, removed the peel, dried, precrushing, ball milling, centrifugation, washing, after drying process
Pretreated reed rod powder；
(2) it weighs reed rod powder, nitrogenous fertilizer, boron fertilizer by the mass ratio of 1:1~3:1~3 to be scattered in deionized water, through 120
Pre- carbonized product is obtained after~160 celsius temperature hydro-thermal process 12~24 hours；
(3) pre- carbonized product and potassium hydroxide are weighed by the mass ratio of 1:1~4, leads to argon gas or nitrogen, it is Celsius with 1~5
Degree/min heating rate be warming up to 700~800 degrees Celsius and keep the temperature 1~2 hour；
(4) using alternately washing 3 times of the hydrochloric acid solution of 3~8% mass ratioes, ethyl alcohol and deionized water, to remove remnants'
Reagent, up to nitrogen, boron doping porous charcoal after 40~60 degrees Celsius of drying.
It is described above in the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal, it is preferred that step
(1) in, using tissue mashing machine carry out precrushing, planetary ball mill carry out ball-milling treatment, rotational speed of ball-mill be 400~500 turns/
Minute, Ball-milling Time is 12~24 hours, and the slurry after ball milling is centrifuged through 3000~5000 revs/min of revolving speed again, sediment
It is alternately and repeatedly washed 3 times through deionized water and dehydrated alcohol, pretreated reed rod powder is dried to obtain in 40~60 degrees Celsius.
Second of preparation method of the nitrogen, boron doping porous charcoal that the present invention provides above-mentioned for electrode of super capacitor,
It includes the following steps:
(1) using natural reed bar as raw material, removed the peel, dried, precrushing, ball milling, centrifugation, washing, after drying process
Pretreated reed rod powder；
(2) it is weighed by 1:1~3:1~3:1~4 mass ratio and takes reed rod powder, nitrogenous fertilizer, boron fertilizer, potassium hydroxide, mixing is equal
Appropriate amount of deionized water is added in even backward system, continues to be evenly stirred until paste, is dried through 40~60 degrees Celsius；
(3) it is transferred in tube furnace, leads to argon gas or nitrogen, be first warming up to 300 with the heating rate of 1~5 degrees celsius/minute
~400 degrees Celsius and heat preservation 1~2 hour, then be warming up to 700~800 degrees Celsius and keep the temperature 1~2 hour；
(4) using alternately washing 3 times of the hydrochloric acid solution of 3~8% mass ratioes, ethyl alcohol and deionized water, to remove remnants'
Reagent, up to nitrogen, boron doping porous charcoal after 40~60 degrees Celsius of drying.
It is described above in the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal, it is preferred that step
(1) in, using tissue mashing machine carry out precrushing, planetary ball mill carry out ball-milling treatment, rotational speed of ball-mill be 400~500 turns/
Minute, Ball-milling Time is 12~24 hours, and the slurry after ball milling is centrifuged through 3000~5000 revs/min of revolving speed again, sediment
It is alternately and repeatedly washed 3 times through deionized water and dehydrated alcohol, pretreated reed rod powder is dried to obtain in 40~60 degrees Celsius.
The third preparation method of the nitrogen, boron doping porous charcoal that the present invention provides above-mentioned for electrode of super capacitor,
Include the following steps:
(1) the fresh and alive reed containing root, the nitrogenous fertilizer of 2~5% mass ratio of Yu Hanyou and the boron fertilizer of 2~5% mass ratioes are dug
It is cultivated 7~30 days in mixed solution；
(2) reed rod of interception step (1) culture, is removed the peel, is dried, precrushing, ball milling, centrifugation, washing, drying process
The reed rod powder of nitrating, boron is obtained afterwards；
(3) the reed rod powder and potassium hydroxide that nitrating, boron are weighed by the mass ratio of 1:1~4, are mixed, are dried；It is transferred to
In tube furnace, leads to argon gas or nitrogen, be first warming up to 300~400 degrees Celsius with the heating rate of 1~5 degrees celsius/minute and keep the temperature
1~2 hour, then be warming up to 700~800 degrees Celsius and keep the temperature 1~2 hour；
(4) using alternately washing 3 times of the hydrochloric acid solution of 3~8% mass ratioes, ethyl alcohol and deionized water, to remove remnants'
Reagent, up to nitrogen, boron doping porous charcoal after 40~60 degrees Celsius of drying.
It is described above in the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal, it is preferred that step
(2) in, using tissue mashing machine carry out precrushing, planetary ball mill carry out ball-milling treatment, rotational speed of ball-mill be 400~500 turns/
Minute, Ball-milling Time is 12~24 hours, and the slurry after ball milling is centrifuged through 3000~5000 revs/min of revolving speed again, sediment
Alternately and repeatedly washed 3 times through deionized water and dehydrated alcohol, dried in 40~60 degrees Celsius nitrating, boron reed rod powder.
Nitrogen of the invention, boron doping porous charcoal can be used as electrode material for super capacitor application.
Natural reed bar of the present invention is derived from natural aquatic reed, mainly rich in crude fibre, crude protein and polysaccharide etc.
Substance.
For step of the present invention (4), the hydrochloric acid solution of 5% mass ratio is used to wash to remove remaining hydroxide
The inorganic salt impurities such as potassium, carbonic acid (hydrogen) potassium and potassium oxide use ethanol washing to remove remaining fluorescence probe impurity.
The present invention is using natural reed bar as carbon source, and nitrogenous fertilizer and boron fertilizer are respectively nitrogen source and boron source, is activated through high temperature carbonization
Nitrogen, boron doping porous charcoal is made in technique, is used for electrode material for super capacitor and has the advantage that
(1) nitrogen obtained by the present invention, boron doping porous charcoal have both point less than 2 nanometer micropores and 2~5 nanometers of mesoporous
Grade three-dimensional porous structure, specific surface area are 1400~1700 meters squared per grams.
(2) present invention obtained by nitrogen, boron doping porous charcoal, N doping atomic ratio be 6~8%, boron mix atomic ratio be 2~
4%, Heteroatom doping amount with higher is based on two kinds of nitrogen, boron heteroatomic synergistic effects, in addition to that can promote porous carbon
The conductivity and raising electrolyte of material can also be obviously improved the fake capacitance characteristic of porous charcoal in the wellability of porous carbon surface,
To make it that there is higher specific capacitance compared with the porous charcoal without Heteroatom doping.
(3) present invention obtained by nitrogen, boron doping porous charcoal as electrode material for super capacitor when, 1 pacify/gram electricity
Under current density with 225~250 faraday/gram specific capacitance, after recycling 5000 charge and discharge, capacitor retain be higher than 95%, In
Under the power density of 500 watts/kilogram with 30~35 watt-hours/kilogram energy density, therefore have very wide market answer
Use prospect.
Reed in the present invention is distributed in irrigation canals and ditches, river levee, natural pond all over the world as a kind of natural products cheap and easy to get
Pool is easy to cultivate and acquire.Important component of the reed rod as reed, mainly contains crude fibre, crude protein and polysaccharide etc.
Substance is a kind of ideal porous carbon feedstock.Using common commercially available nitrogenous fertilizer, boron fertilizer as nitrogen source and boron source, it is produced into
This is low and is easier to the industrialization of the technology of the present invention.
Nitrogen produced by the present invention for electrode of super capacitor, boron doping porous charcoal, in addition to biggish specific surface
The three-dimensional porous structure of product and classification, can be improved hole utilization rate to obtain higher electric double layer capacitance characteristic, additionally has
There are higher nitrogen, boron doping amount, more hole surfaces polarization site, surface wettability can be provided and surface is nitrogenous, boron function
Group, to improve the electric double layer capacitance and fake capacitance characteristic of porous carbon material simultaneously.Take nitrogen, the boron doping of invention
With high specific capacitance and energy density when porous charcoal is applied to electrode of super capacitor.
Detailed description of the invention
Fig. 1 is the field emission scanning electron microscope figure of nitrogen of the invention, boron doping porous charcoal.
Fig. 2 is nitrogen adsorption/desorption isothermal curve of nitrogen of the invention, boron doping porous charcoal.
Fig. 3 is the x-ray photoelectron spectroscopy of nitrogen of the invention, boron doping porous charcoal, and inserting table is each element content.
Fig. 4 is the cyclic voltammetry curve of nitrogen obtained by the present invention, boron doping porous charcoal.
Fig. 5 is the constant current charge-discharge curve of nitrogen obtained by the present invention, boron doping porous charcoal under two electrode systems, electricity
Current density be respectively 1,2,5 and 10 peace/gram.
Fig. 6 is the charge and discharge cycles stability curve of nitrogen obtained by the present invention, boron doping porous charcoal.
Specific embodiment
Following embodiments are further explanations for the content of present invention using as the explaination to the technology of the present invention content, but
Substantive content of the invention is not limited in described in following embodiments, those skilled in the art can with and should know appoint
What simple change or replacement based on true spirit should belong to protection scope of the presently claimed invention.
Embodiment 1
(1) reed rod is intercepted, peeling is dried, using tissue mashing machine by its precrushing, using deionized water as dispersing agent,
Using planetary ball mill by the further ball-milling treatment of the reed rod of precrushing, revolving speed is 500 revs/min, Ball-milling Time 24
Hour.
(2) slurry after ball milling is centrifuged through 5000 revs/min of revolving speed, sediment through deionized water and dehydrated alcohol repeatedly
Alternately washing 3 times, dry to obtain pretreated reed rod powder in 50 degrees Celsius.
(3) by the mass ratio of 1:2:2 weigh reed rod powder, urea ammonium nitrogenous fertilizer (it is nitrogenous >=30%, the red cubic share in middle salt Anhui
Co., Ltd), boron fertilizer (boric acid sodium salt >=99%, boracic >=15%, Anhui Nongwang Agricultural Technology Development Co., Ltd) dispersion
In deionized water, in hydrothermal reaction kettle, 160 degrees Centigrades 12 hours, sediment is anti-through deionized water and dehydrated alcohol
Complex Alternating washs 3 times, up to pre- carbonized product after 50 degrees Celsius of drying.
(4) pre- carbonized product and potassium hydroxide are weighed by the mass ratio of 1:3, is added after being uniformly mixed into system and goes in right amount
Ionized water continues to be evenly stirred until paste, through 50 degrees Celsius dry, be transferred in tube furnace, lead to argon atmosphere, with 2 degrees Celsius/
The heating rate of minute is warming up to 700 degrees Celsius and keeps the temperature 1 hour.
(5) it after being cooled to room temperature, is alternately washed 3 times using the hydrochloric acid solution, ethyl alcohol and deionized water of 5% mass ratio,
Up to nitrogen, boron doping porous charcoal after 50 degrees Celsius of drying.
As shown in Figure 1, be the field emission scanning electron microscope figure of nitrogen obtained by the present invention, boron doping porous charcoal,
With significant three-dimensional porous structure.
As shown in Fig. 2, be nitrogen adsorption/desorption isothermal curve of nitrogen obtained by the present invention, boron doping porous charcoal, ratio
Surface area is up to 1650 meters squared per grams.
As shown in figure 3, be the x-ray photoelectron spectroscopy of nitrogen obtained by the present invention, boron doping porous charcoal, wherein N doping
Amount is 7.22%, boron doping amount 3.23%.
As shown in figure 4, be the cyclic voltammetry curve of nitrogen obtained by the present invention, boron doping porous charcoal, wherein nitrogen, boron doping
Porous charcoal relatively has higher specific capacitance undoped with porous charcoal, and nitrogen, the significant oxidation peak of boron doping porous charcoal illustrate that it is preferable
Fake capacitance characteristic.
As shown in figure 5, being the constant current charge-discharge of nitrogen obtained by the present invention, boron doping porous charcoal under two electrode systems
Curve.According to formula Cs=I × Δ t/ (m × Δ V) can calculate quality specific capacitance Cs(faraday/gram), wherein I (peace) is to put
Electric current, Δ t (second) are discharge time, and m (gram) is the gross mass of active material on two electrodes, and Δ V (volt) is discharge potential window.
Be computed can obtain current density be 1 peace/gram when, the present invention obtained by nitrogen, boron doping porous charcoal quality specific capacitance be 242 methods
Draw the/gram.In addition, even if 10 peaces/gram high current density under, nitrogen obtained by the present invention, boron doping porous charcoal still has
Up to 235 faraday/gram specific capacitance, thus have excellent rate charge-discharge ability.In addition, according to formula Em=0.5 × Cs
×(ΔV)2And Pm=Em/ Δ t can calculate energy density Em(watt-hour/kilogram) and power density Pm(watt/kilogram), Cs(farad
The/gram) it is quality specific capacitance, Δ V (volt) is discharge potential window, and Δ t (second) is discharge time.When power density is 500 watts/thousand
Gram when, energy density up to 33.6 watt-hours/kilogram, thus have very wide market application prospect.
As shown in fig. 6, being the charge and discharge cycles stability curve of nitrogen obtained by the present invention, boron doping porous charcoal.10
Peace/gram current density under, after undergoing 5000 circulation constant current charge-discharges to test, capacitor still retains initial capacitance
96% or so, coulombic efficiency is also basically stable at 99% or more after 150 circulations of experience, shows excellent stable circulation
Property, solid foundation is provided for its commercial applications.
Embodiment 2
(1) reed rod is intercepted, peeling is dried, using tissue mashing machine by its precrushing, using deionized water as dispersing agent,
Using planetary ball mill by the further ball-milling treatment of the reed rod of precrushing, revolving speed is 500 revs/min, Ball-milling Time 24
Hour.
(2) slurry after ball milling is centrifuged through 5000 revs/min of revolving speed, sediment through deionized water and dehydrated alcohol repeatedly
Alternately washing 3 times, dry to obtain pretreated reed rod powder in 50 degrees Celsius.
(3) reed rod powder, nitrogenous fertilizer, boron fertilizer, potassium hydroxide are weighed by the mass ratio of 1:2:2:3, to system after being uniformly mixed
Middle addition appropriate amount of deionized water, continues to be evenly stirred until paste, dries, is transferred in tube furnace through 50 degrees Celsius, leads to argon gas gas
Atmosphere is first warming up to 300 degrees Celsius with the heating rate of 2 degrees celsius/minutes and keeps the temperature 1 hour, then is warming up to 700 degrees Celsius and protects
Temperature 1 hour.
(4) it after being cooled to room temperature, is alternately washed 3 times using the hydrochloric acid solution, ethyl alcohol and deionized water of 5% mass ratio,
Up to nitrogen, boron doping porous charcoal after 50 degrees Celsius of drying.
Obtained nitrogen, boron doping porous charcoal have three-dimensional porous structure, and specific surface area is up to 1500 meters squared per grams,
N doping amount is 6.72%, and boron doping amount 3.15% has both the mixing capacitance characteristic of electric double layer capacitance and fake capacitance.1 pacify/
Gram current density under, the nitrogen, boron doping porous charcoal quality specific capacitance be 225 faraday/gram, energy density be 31.3 watts
When/kilogram.After cycle charge-discharge 5000 times, capacitor reservation is still higher than 97% for the nitrogen, boron doping porous charcoal, has preferable city
Field application prospect.
Embodiment 3
(1) the fresh and alive reed containing root is dug, the boron fertilizer mixing of the nitrogenous fertilizer and 5% mass ratio of 5% mass ratio of Yu Hanyou is molten
After cultivating 15 days in liquid, reed rod is intercepted, peeling is adopted its precrushing using deionized water as dispersing agent using tissue mashing machine
With planetary ball mill by the further ball-milling treatment of the reed rod of precrushing, revolving speed is 500 revs/min, and Ball-milling Time is 24 small
When.
(2) slurry after ball milling is centrifuged through 5000 revs/min of revolving speed, sediment through deionized water and dehydrated alcohol repeatedly
Alternately washing 3 times, dry to obtain pretreated reed rod powder in 50 degrees Celsius.
(3) reed rod powder and potassium hydroxide are weighed by the mass ratio of 1:3, be uniformly mixed after into system be added in right amount go from
Sub- water continues to be evenly stirred until paste, dries, is transferred in tube furnace through 50 degrees Celsius, leads to argon atmosphere, with 2 degree mins Celsius
The heating rate of clock is first warming up to 300 degrees Celsius and keeps the temperature 1 hour, then is warming up to 700 degrees Celsius and keeps the temperature 1 hour.
(4) it after being cooled to room temperature, is alternately washed 3 times using the hydrochloric acid solution, ethyl alcohol and deionized water of 5% mass ratio,
Up to nitrogen, boron doping porous charcoal after 50 degrees Celsius of drying.
The same porous structure with classification of obtained nitrogen, boron doping porous charcoal, aperture is mainly distributed on 1~5 and receives
Rice, N doping amount are 5.78%, and boron doping amount 1.92% has both the mixing capacitance characteristic of electric double layer capacitance and fake capacitance.1
Peace/gram current density under, the nitrogen, boron doping porous charcoal quality specific capacitance be 231 faraday/gram, energy density be 32 watts
When/kilogram.After cycle charge-discharge 5000 times, capacitor reservation is still higher than 95% for the nitrogen, boron doping porous charcoal, has more excellent
Capacitive property, can preferably introduce application to the market.
Claims (7)
1. a kind of nitrogen for electrode of super capacitor, boron doping porous charcoal, which is characterized in that it is with natural reed bar for original
Material is made respectively using nitrogenous fertilizer and boron fertilizer as nitrogen source and boron source through carbonization-activation technique, which has both micropore in
The classification three dimensional pore structures in hole, for pore-size distribution at 1~5 nanometer, specific surface area is 1400~1700 meters squared per grams, and nitrating is former
For son than being 6~8%, boron-doping atomic ratio is 2~4%；When as electrode material for super capacitor, 1 peace/gram current density
Down with 225~250 faraday/gram specific capacitance, after recycling 5000 charge and discharge, capacitor retain be higher than 95%；It is described natural
Reed rod removed the peel, dried, precrushing, ball milling, centrifugation, washing, after drying process pretreated reed rod powder.
2. for the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal described in claim 1, which is characterized in that
Include the following steps:
(1) using natural reed bar as raw material, removed the peel, dried, precrushing, ball milling, centrifugation, washing, after drying process locate in advance
The reed rod powder of reason；
(2) it weighs reed rod powder, nitrogenous fertilizer, boron fertilizer by the mass ratio of 1:1~3:1~3 to be scattered in deionized water, through 120~160
Pre- carbonized product is obtained after celsius temperature hydro-thermal process 12~24 hours；
(3) pre- carbonized product and potassium hydroxide are weighed by the mass ratio of 1:1~4, leads to argon gas or nitrogen, with 1~5 degree min Celsius
The heating rate of clock is warming up to 700~800 degrees Celsius and keeps the temperature 1~2 hour；
(4) using alternately washing 3 times of the hydrochloric acid solution of 3~8% mass ratioes, ethyl alcohol and deionized water, to remove remaining reagent,
Up to nitrogen, boron doping porous charcoal after 40~60 degrees Celsius of drying.
3. as claimed in claim 2 for the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal, feature exists
In in step (1), using tissue mashing machine's progress precrushing, planetary ball mill carries out ball-milling treatment, rotational speed of ball-mill 400
~500 revs/min, Ball-milling Time is 12~24 hours, slurry after ball milling again through 3000~5000 revs/min revolving speed from
The heart, sediment alternately and repeatedly wash 3 times through deionized water and dehydrated alcohol, and pretreated reed is dried to obtain in 40~60 degrees Celsius
Bar powder.
4. for the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal described in claim 1, which is characterized in that
Include the following steps:
(1) using natural reed bar as raw material, removed the peel, dried, precrushing, ball milling, centrifugation, washing, after drying process locate in advance
The reed rod powder of reason；
(2) reed rod powder, nitrogenous fertilizer, boron fertilizer, potassium hydroxide are weighed by 1:1~3:1~3:1~4 mass ratio, be uniformly mixed backward
Appropriate amount of deionized water is added in system, continues to be evenly stirred until paste, is dried through 40~60 degrees Celsius；
(3) it is transferred in tube furnace, leads to argon gas or nitrogen, it is warming up to 300 first with the heating rate of 1~5 degrees celsius/minute~
400 degrees Celsius and heat preservation 1~2 hour, then be warming up to 700~800 degrees Celsius and keep the temperature 1~2 hour；
(4) using alternately washing 3 times of the hydrochloric acid solution of 3~8% mass ratioes, ethyl alcohol and deionized water, to remove remaining reagent,
Up to nitrogen, boron doping porous charcoal after 40~60 degrees Celsius of drying.
5. as claimed in claim 4 for the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal, feature exists
In in step (1), using tissue mashing machine's progress precrushing, planetary ball mill carries out ball-milling treatment, rotational speed of ball-mill 400
~500 revs/min, Ball-milling Time is 12~24 hours, slurry after ball milling again through 3000~5000 revs/min revolving speed from
The heart, sediment alternately and repeatedly wash 3 times through deionized water and dehydrated alcohol, and pretreated reed is dried to obtain in 40~60 degrees Celsius
Bar powder.
6. for the nitrogen of electrode of super capacitor, the preparation method of boron doping porous charcoal described in claim 1, which is characterized in that
Include the following steps:
(1) the fresh and alive reed containing root, the boron fertilizer mixing of the nitrogenous fertilizer and 2~5% mass ratioes of 2~5% mass ratio of Yu Hanyou are dug
It is cultivated 7~30 days in solution；
(2) reed rod of interception step (1) culture, removed the peel, dried, precrushing, ball milling, centrifugation, washing, after drying process
The reed rod powder of nitrating, boron；
(3) the reed rod powder and potassium hydroxide that nitrating, boron are weighed by the mass ratio of 1:1~4, are mixed, are dried；It is transferred to tubular type
In furnace, lead to argon gas or nitrogen, be first warming up to 300~400 degrees Celsius with the heating rate of 1~5 degrees celsius/minute and keep the temperature 1~2
Hour, then be warming up to 700~800 degrees Celsius and keep the temperature 1~2 hour；
(4) using alternately washing 3 times of the hydrochloric acid solution of 3~8% mass ratioes, ethyl alcohol and deionized water, to remove remaining reagent,
Up to nitrogen, boron doping porous charcoal after 40~60 degrees Celsius of drying.
7. the described in claim 1 or nitrogen that is obtained by any one of claim 2~6 preparation method, boron doping are porous
Application of the charcoal as electrode material for super capacitor.
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| CN108597910A (en) * | 2018-04-16 | 2018-09-28 | 桂林电子科技大学 | A kind of nitrogen boron codope porous carbon materials and its preparation method and application |
| CN109110759A (en) * | 2018-11-07 | 2019-01-01 | 河南师范大学 | A kind of preparation method of nitrogen, boron codope porous carbon materials |
| CN109251031A (en) * | 2018-11-23 | 2019-01-22 | 福建农林大学 | A kind of method of microwave assisted aqueous extraction hot preparation for the nitrogen co-doped porous carbon material of boron of supercapacitor |
| CN111285368B (en) * | 2018-12-10 | 2022-05-27 | 河南工程学院 | Preparation method of nitrogen-boron double-doped porous hollow carbon nano-capsule material |
| CN109734083B (en) * | 2019-01-30 | 2020-07-03 | 河南工程学院 | Highly graphitized boron-doped dumbbell-shaped micro mesoporous carbon and preparation method thereof |
| CN110028053A (en) * | 2019-05-16 | 2019-07-19 | 济宁医学院 | A kind of preparation method and applications of high nitrogen doped amount nano cages material |
| CN110240160B (en) * | 2019-06-26 | 2021-03-02 | 陕西科技大学 | Preparation method of boron-doped biomass porous carbon nano electrode material for sodium ion battery |
| CN111137886A (en) * | 2019-11-19 | 2020-05-12 | 南京工程学院 | Method for preparing electrode material by aquatic plant |
| CN115036152B (en) * | 2022-07-09 | 2023-04-18 | 电子科技大学 | Hollow spherical boron-carbon-nitrogen material and preparation method thereof |
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