CN107010624A - A kind of nitrogen, boron for electrode of super capacitor adulterates porous charcoal and preparation method thereof - Google Patents
A kind of nitrogen, boron for electrode of super capacitor adulterates porous charcoal and preparation method thereof Download PDFInfo
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- CN107010624A CN107010624A CN201710269708.0A CN201710269708A CN107010624A CN 107010624 A CN107010624 A CN 107010624A CN 201710269708 A CN201710269708 A CN 201710269708A CN 107010624 A CN107010624 A CN 107010624A
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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
Adulterated porous charcoal and preparation method thereof the invention discloses a kind of nitrogen, boron for electrode of super capacitor, belong to energy and material and applied technical field.The present invention is, using natural reed bar as carbon source, respectively using nitrogenous fertilizer and boron fertilizer as nitrogen source and boron source, to be made through carbonization-activation technique.Nitrogen, boron doping porous charcoal obtained by the present invention have the classification three dimensional pore structures of micropore and mesopore concurrently, 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%.During as electrode material for super capacitor, its 1 peace/gram current density under have 225~250 faraday/gram specific capacitance, circulate 5000 discharge and recharges after, electric capacity retain be higher than 95%, under the power density of 500 watts/kilogram have 30~35 watt-hours/kilogram energy density.
Description
Technical field
The invention belongs to energy and material and applied technical field, and in particular to a kind of nitrogen for electrode of super capacitor,
Boron doping porous charcoal and preparation method thereof.
Background technology
Porous charcoal due to specific surface area is big, pore structure adjustable, chemical stability it is good with the low advantage of cost into
For the preferred electrode material of ultracapacitor.Porous carbon electrode is mainly formed at electrode/electrolyte interface in ultracapacitor
Electric double layer stores energy, and therefore, the absorbent charcoal material of high-efficiency energy-storage should possess the bigger serface for being conducive to charge accumulated
With the pore structure for being easy to electrolyte wetting and ion fast transferring.Research finds that the porous charcoal of Heteroatom doping is more traditional more
Hole charcoal has more excellent chemical property.
The raw material that preparation porous charcoal is used is various, and organic molecule, polymer, petroleum coke, natural products etc. are
Carbon source can be used as.
The patent of such as Application No. 201310297709.8 disclose it is a kind of prepared using complex salicylate it is super
The method of capacitor porous charcoal, obtained porous charcoal has 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 technology is cumbersome, and structure is difficult to control, it is difficult to obtain scale application.
The patent of such as Application No. 201410508582.4 discloses a kind of preparation method of porous carbon material, specifically relates to
And a kind of method that Heat-resistant polymer film leftover pieces using difficult reclaiming prepare porous carbon electrode material, although use
Cheap thin polymer film leftover pieces are carbon source, and obtained porous charcoal specific surface area 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 should.
The patent of such as Application No. 201410506124.7 discloses a kind of preparation method of super capacitor porous charcoal,
Petroleum coke, acrylic resin etc. are used for raw material, porous charcoal is made after high-temperature activation, its 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. reports one kind using phenol and formaldehyde as raw material, melamine and boron
Acid is nitrogen source and boron source, then using silica as template, the nitrogen with hierarchy, boron is prepared for after multi step strategy technique common
The porous charcoal of doping, although with 189~304 faraday/gram specific capacitance, but its specific surface area is relatively low, only 648 squares
Rice/gram, and the virose chemical reagent such as the phenol and formaldehyde used, easily environment is polluted, clean energy resource is not met
Development trend.
It is numerous can as prepare porous charcoal raw material in, natural products because its it is widely distributed, cheap and easy to get the advantages of
And come by extensive popularization.
The patent of such as Application No. 201510611801.6 discloses the side that super porous Carbon Materials are prepared with persimmon pericarp
Method, uses persimmon pericarp for raw material, porous charcoal is made after carbonization, activation, 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.
The content of the invention
It is an object of the invention to provide a kind of can be applied to electrode material for super capacitor, with quality it is light, compare surface
Porous charcoal and preparation method thereof that product is big, hole is classified and the high nitrogen of electro-chemical activity, boron adulterate.
A kind of nitrogen, boron for electrode of super capacitor that the present invention is provided adulterates porous charcoal, and it is with natural reed bar
For raw material, respectively using nitrogenous fertilizer and boron fertilizer as nitrogen source and boron source, it is made through carbonization-activation technique, the porous carbon material has micropore concurrently
With the classification three dimensional pore structures of mesopore, 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.It is used as super capacitor electrode
During the material of pole, its 1 peace/gram current density under have 225~250 faraday/gram specific capacitance, circulate 5000 discharge and recharges
Afterwards, electric capacity retain be higher than 95%, under the power density of 500 watts/kilogram have 30~35 watt-hours/kilogram energy density.
A kind of preparation method for porous charcoal of being adulterated the invention provides above-mentioned nitrogen, boron for electrode of super capacitor, its
Comprise the steps：
(1) using natural reed bar as raw material, through removing the peel, drying, precrushing, ball milling, centrifugation, washing, after drying process
The reed rod powder of pretreatment；
(2) 1 is pressed:1~3:1~3 mass ratio weighs reed rod powder, nitrogenous fertilizer, boron fertilizer and is scattered in deionized water, through 120
Pre- carbonized product is obtained after~160 celsius temperature hydro-thermal process 12~24 hours；
(3) 1 is pressed:1~4 mass ratio weighs pre- carbonized product and potassium hydroxide, leads to argon gas or nitrogen, Celsius with 1~5
Degree/min heating rate be warming up to 700~800 degrees Celsius and be incubated 1~2 hour；
(4) using hydrochloric acid solution, ethanol and deionized water alternately washing 3 times of 3~8% mass ratioes, to remove remnants'
Reagent, produces nitrogen, boron doping porous charcoal after being dried in 40~60 degrees Celsius.
Nitrogen, boron described above for electrode of super capacitor adulterate porous charcoal preparation method in, 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 rotating speed again, sediment
Alternately and repeatedly washed 3 times through deionized water and absolute ethyl alcohol, the reed rod powder that must be pre-processed is dried in 40~60 degrees Celsius.
Second of preparation method of porous charcoal of being adulterated the invention provides above-mentioned nitrogen, boron for electrode of super capacitor,
It comprises the steps：
(1) using natural reed bar as raw material, through removing the peel, drying, precrushing, ball milling, centrifugation, washing, after drying process
The reed rod powder of pretreatment；
(2) 1 is pressed:1~3:1~3:1~4 mass ratio, which is weighed, takes reed rod powder, nitrogenous fertilizer, boron fertilizer, potassium hydroxide, and mixing is equal
Appropriate amount of deionized water is added in even backward system, continues to be evenly stirred until pasty state, through 40~60 degrees Celsius of drying；
(3) it is transferred in tube furnace, leads to argon gas or nitrogen, 300 are first warming up to the heating rate of 1~5 degrees celsius/minute
~400 degrees Celsius and be incubated 1~2 hour, then be warming up to 700~800 degrees Celsius and be incubated 1~2 hour；
(4) using hydrochloric acid solution, ethanol and deionized water alternately washing 3 times of 3~8% mass ratioes, to remove remnants'
Reagent, produces nitrogen, boron doping porous charcoal after being dried in 40~60 degrees Celsius.
Nitrogen, boron described above for electrode of super capacitor adulterate porous charcoal preparation method in, 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 rotating speed again, sediment
Alternately and repeatedly washed 3 times through deionized water and absolute ethyl alcohol, the reed rod powder that must be pre-processed is dried in 40~60 degrees Celsius.
The third preparation method for porous charcoal of being adulterated the invention provides above-mentioned nitrogen, boron for electrode of super capacitor,
Comprise the following steps：
(1) the fresh and alive reed containing coring is dug, in the nitrogenous fertilizer containing 2~5% mass ratioes and the boron fertilizer of 2~5% mass ratioes
Cultivated 7~30 days in mixed solution；
(2) interception step (1) culture reed rod, through removing the peel, drying, precrushing, ball milling, centrifugation, washing, drying process
Nitrating, the reed rod powder of boron are obtained afterwards；
(3) 1 is pressed:1~4 mass ratio weighs the reed rod powder and potassium hydroxide of nitrating, boron, blended, drying；It is transferred to
In tube 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 be incubated
1~2 hour, then be warming up to 700~800 degrees Celsius and be incubated 1~2 hour；
(4) using hydrochloric acid solution, ethanol and deionized water alternately washing 3 times of 3~8% mass ratioes, to remove remnants'
Reagent, produces nitrogen, boron doping porous charcoal after being dried in 40~60 degrees Celsius.
Nitrogen, boron described above for electrode of super capacitor adulterate porous charcoal preparation method in, 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 rotating speed again, sediment
Alternately and repeatedly washed 3 times through deionized water and absolute ethyl alcohol, nitrating, the reed rod powder of boron are dried to obtain in 40~60 degrees Celsius.
The nitrogen of the present 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.
Material.
For step of the present invention (4), the hydrochloric acid solution of 5% mass ratio is used to wash to remove remnants hydroxide
The inorganic salt impurities such as potassium, carbonic acid (hydrogen) potassium and potassium oxide, use ethanol washing to remove remnants fluorescence probe impurity.
The present invention is that, using natural reed bar as carbon source, nitrogenous fertilizer and boron fertilizer are respectively nitrogen source and boron source, are activated through high temperature carbonization
Nitrogen, boron doping porous charcoal is made in technique, and it is used for electrode material for super capacitor and had the advantage that：
(1) nitrogen obtained by the present invention, boron doping porous charcoal, have point less than 2 nanometer micropores and 2~5 nanometers of mesopores concurrently
Level three-dimensional porous structure, specific surface area is 1400~1700 meters squared per grams.
(2) nitrogen obtained by the present invention, boron doping porous charcoal, N doping atomic ratio is 6~8%, boron mix atomic ratio for 2~
4%, with higher Heteroatom doping amount, based on nitrogen, the heteroatomic synergy of two kinds of boron, except porous carbon can be lifted
The electrical 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,
So that it has higher specific capacitance compared with the porous charcoal without Heteroatom doping.
(3) present invention obtained by nitrogen, boron adulterate porous charcoal as electrode material for super capacitor when, 1 peace/gram electricity
Under current density have 225~250 faraday/gram specific capacitance, circulation 5000 discharge and recharges after, electric capacity retain be higher than 95%,
Have under the power density of 500 watts/kilogram 30~35 watt-hours/kilogram energy density, therefore should with very wide market
Use prospect.
Reed in the present invention is distributed in irrigation canals and ditches all over the world, river levee, natural pond as a kind of natural products cheap and easy to get
Pool, it is easy to culture and collection.Reed rod mainly contains crude fibre, crude protein and polysaccharide etc. as the important component of reed
Material, 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, boron produced by the present invention for electrode of super capacitor adulterates porous charcoal, except with larger ratio surface
Product and the three-dimensional porous structure of classification, can improve hole utilization rate to obtain higher electric double layer capacitance characteristic, additionally have
There are higher nitrogen, boron doping amount, more hole surfaces polarization sites, surface wettability can be provided and surface is nitrogenous, boron function
Group, so as to improve the electric double layer capacitance and fake capacitance characteristic of porous carbon material simultaneously.Take nitrogen, the boron doping of invention
Porous charcoal is applied to have high specific capacitance and energy density during electrode of super capacitor.
Brief description of the drawings
Fig. 1 is the nitrogen of the present invention, the field emission scanning electron microscope figure of boron doping porous charcoal.
Fig. 2 is the nitrogen of the present invention, nitrogen adsorption/desorption isothermal curve of boron doping porous charcoal.
Fig. 3 is the nitrogen of the present invention, the x-ray photoelectron power spectrum of boron doping porous charcoal, and it is each element content to insert table.
Fig. 4 is nitrogen, the cyclic voltammetry curve of boron doping porous charcoal obtained by the present invention.
Fig. 5 is the constant current charge-discharge curve of nitrogen, boron doping porous charcoal under two electrode systems obtained by the present invention, electricity
Current density be respectively 1,2,5 and 10 peace/gram.
Fig. 6 is nitrogen, the charge and discharge cycles stability curve of boron doping porous charcoal obtained by the present invention.
Embodiment
Following embodiments are further illustrating using as the explaination to the technology of the present invention content for present invention, but
The present invention substantive content be not limited in described in following embodiments, one of ordinary skill in the art can with and should know appoint
What simple change or replacement based on true spirit all should belong to protection domain 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 dispersant,
Using planetary ball mill by the further ball-milling treatment of the reed rod of precrushing, rotating speed is 500 revs/min, and Ball-milling Time is 24
Hour.
(2) slurry after ball milling is centrifuged through 5000 revs/min of rotating speed, sediment through deionized water and absolute ethyl alcohol repeatedly
Alternately washing 3 times, the reed rod powder that must be pre-processed is dried in 50 degrees Celsius.
(3) 1 is pressed:2:2 mass ratio weighs reed rod powder, urea ammonium nitrogenous fertilizer (nitrogenous >=30%, the middle red cubic share in salt Anhui
Co., Ltd), boron fertilizer (boric acid sodium salt >=99%, boracic >=15%, Anhui Nongwang Agricultural Technology Development Co., Ltd) disperse
In deionized water, in hydrothermal reaction kettle, 160 degrees Centigrades 12 hours, sediment is anti-through deionized water and absolute ethyl alcohol
Complex Alternating is washed 3 times, and pre- carbonized product is produced after being dried in 50 degrees Celsius.
(4) 1 is pressed:3 mass ratio weighs pre- carbonized product and potassium hydroxide, is well mixed to add in backward system and goes in right amount
Ionized water, continues to be evenly stirred until pasty state, through 50 degrees Celsius drying, be transferred in tube furnace, lead to argon gas atmosphere, with 2 degrees Celsius/
The heating rate of minute is warming up to 700 degrees Celsius and is incubated 1 hour.
(5) it is cooled to after room temperature, is alternately washed 3 times using the hydrochloric acid solution, ethanol and deionized water of 5% mass ratio,
Nitrogen, boron doping porous charcoal are produced after being dried in 50 degrees Celsius.
As shown in figure 1, be nitrogen, the field emission scanning electron microscope figure of boron doping porous charcoal obtained by the present invention, its
With significant three-dimensional porous structure.
As shown in Fig. 2 being nitrogen, the nitrogen adsorption/desorption isothermal curve of boron doping porous charcoal obtained by the present invention, it compares
Surface area is up to 1650 meters squared per grams.
As shown in figure 3, being that nitrogen obtained by the present invention, boron adulterate the x-ray photoelectron power spectrum of porous charcoal, wherein N doping
Measure as 7.22%, boron doping amount is 3.23%.
As shown in figure 4, being nitrogen, the cyclic voltammetry curve of boron doping porous charcoal obtained by the present invention, wherein nitrogen, boron doping
Porous charcoal has higher specific capacitance compared with undoped with porous charcoal, and nitrogen, the boron doping significant oxidation peak of porous charcoal illustrate that its is preferable
Fake capacitance characteristic.
As shown in figure 5, being the constant current charge-discharge of nitrogen, boron doping porous charcoal under two electrode systems obtained by the present invention
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) is 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 obtaining current density for 1 peace/gram when, nitrogen, the quality specific capacitance of boron doping porous charcoal obtained by the present invention are 242 methods
Draw the/gram.In addition, even in 10 peace/gram high current density under, the present invention obtained by nitrogen, boron doping porous charcoal still have
Up to 235 faraday/gram specific capacitance, thus with 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 with very wide market application foreground.
As shown in fig. 6, being nitrogen, the charge and discharge cycles stability curve of boron doping porous charcoal obtained by the present invention.10
Peace/gram current density under, undergo 5000 times circulation constant current charge-discharges test after, capacitor still retains initial capacitance
96% or so, coulombic efficiency is also basically stable at more than 99% after 150 circulations of experience, shows excellent stable circulation
Property, provide solid foundation 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 dispersant,
Using planetary ball mill by the further ball-milling treatment of the reed rod of precrushing, rotating speed is 500 revs/min, and Ball-milling Time is 24
Hour.
(2) slurry after ball milling is centrifuged through 5000 revs/min of rotating speed, sediment through deionized water and absolute ethyl alcohol repeatedly
Alternately washing 3 times, the reed rod powder that must be pre-processed is dried in 50 degrees Celsius.
(3) 1 is pressed:2:2:3 mass ratio weighs reed rod powder, nitrogenous fertilizer, boron fertilizer, potassium hydroxide, is well mixed backward system
Middle addition appropriate amount of deionized water, continues to be evenly stirred until pasty state, through 50 degrees Celsius of drying, is transferred in tube furnace, leads to argon gas gas
Atmosphere, is first warming up to 300 degrees Celsius with the heating rate of 2 degrees celsius/minutes and is incubated 1 hour, then be warming up to 700 degrees Celsius and protect
Temperature 1 hour.
(4) it is cooled to after room temperature, is alternately washed 3 times using the hydrochloric acid solution, ethanol and deionized water of 5% mass ratio,
Nitrogen, boron doping porous charcoal are produced after being dried in 50 degrees Celsius.
Obtained nitrogen, boron doping porous charcoal have three-dimensional porous structure, and its specific surface area is up to 1500 meters squared per grams,
N doping amount is 6.72%, and boron doping amount is 3.15%, has the mixing capacitance characteristic of electric double layer capacitance and fake capacitance concurrently.1 pacify/
Gram current density under, the nitrogen, boron doping porous charcoal quality specific capacitance for 225 faraday/gram, energy density be 31.3 watts
When/kilogram.The nitrogen, boron adulterate porous charcoal after cycle charge-discharge 5000 times, and electric capacity, which retains, remains above 97%, with preferable city
Field application prospect.
Embodiment 3
(1) the fresh and alive reed containing coring is dug, it is molten in the boron fertilizer mixing of the nitrogenous fertilizer containing 5% mass ratio and 5% mass ratio
After being cultivated 15 days in liquid, reed rod is intercepted, peeling, using tissue mashing machine by its precrushing, using deionized water as dispersant, is adopted
With planetary ball mill by the further ball-milling treatment of the reed rod of precrushing, rotating 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 rotating speed, sediment through deionized water and absolute ethyl alcohol repeatedly
Alternately washing 3 times, the reed rod powder that must be pre-processed is dried in 50 degrees Celsius.
(3) 1 is pressed:3 mass ratio weighs reed rod powder and potassium hydroxide, be well mixed in backward system add it is appropriate go from
Sub- water, continues to be evenly stirred until pasty state, through 50 degrees Celsius of drying, is transferred in tube furnace, leads to argon gas atmosphere, with 2 degree mins Celsius
The heating rate of clock is first warming up to 300 degrees Celsius and is incubated 1 hour, then is warming up to 700 degrees Celsius and is incubated 1 hour.
(4) it is cooled to after room temperature, is alternately washed 3 times using the hydrochloric acid solution, ethanol and deionized water of 5% mass ratio,
Nitrogen, boron doping porous charcoal are produced after being dried in 50 degrees Celsius.
The same loose structure with classification of obtained nitrogen, boron doping porous charcoal, aperture is mainly distributed on 1~5 and received
Rice, N doping amount is 5.78%, and boron doping amount is 1.92%, has the mixing capacitance characteristic of electric double layer capacitance and fake capacitance concurrently.1
Peace/gram current density under, the nitrogen, boron doping porous charcoal quality specific capacitance for 231 faraday/gram, energy density be 32 watts
When/kilogram.The nitrogen, boron adulterate porous charcoal after cycle charge-discharge 5000 times, and electric capacity, which retains, remains above 95%, with more excellent
Capacitive property, can preferably introduce application to the market.
Claims (7)
- The porous charcoal 1. a kind of nitrogen, boron for electrode of super capacitor adulterates, it is characterised in that it is using natural reed bar as original Material, respectively using nitrogenous fertilizer and boron fertilizer as nitrogen source and boron source, is made, the porous carbon material has micropore concurrently with through carbonization-activation technique The classification three dimensional pore structures in hole, pore-size distribution is at 1~5 nanometer, and specific surface area is 1400~1700 meters squared per grams, and nitrating is former Son is than being 6~8%, and boron-doping atomic ratio is 2~4%.
- The preparation method of porous charcoal 2. nitrogen, the boron described in claim 1 for electrode of super capacitor adulterate, it is characterised in that Comprise the following steps：(1) using natural reed bar as raw material, through removing the peel, drying, precrushing, ball milling, centrifugation, washing, after drying process locate in advance The reed rod powder of reason；(2) 1 is pressed:1~3:1~3 mass ratio weighs reed rod powder, nitrogenous fertilizer, boron fertilizer and is scattered in deionized water, through 120~160 Celsius temperature hydro-thermal process obtains pre- carbonized product after 12~24 hours；(3) 1 is pressed:1~4 mass ratio weighs pre- carbonized product and potassium hydroxide, 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 is incubated 1~2 hour；(4) using hydrochloric acid solution, ethanol and deionized water alternately washing 3 times of 3~8% mass ratioes, to remove remnants reagent, Nitrogen, boron doping porous charcoal are produced after being dried in 40~60 degrees Celsius.
- The preparation method of porous charcoal 3. nitrogen, boron as claimed in claim 2 for electrode of super capacitor adulterates, its feature exists In in step (1), using tissue mashing machine's progress precrushing, planetary ball mill carries out ball-milling treatment, and rotational speed of ball-mill is 400 ~500 revs/min, Ball-milling Time is 12~24 hours, slurry after ball milling again through 3000~5000 revs/min of rotating speed from The heart, sediment is alternately and repeatedly washed 3 times through deionized water and absolute ethyl alcohol, and the reed that must be pre-processed is dried in 40~60 degrees Celsius Bar powder.
- The preparation method of porous charcoal 4. nitrogen, the boron described in claim 1 for electrode of super capacitor adulterate, it is characterised in that Comprise the following steps：(1) using natural reed bar as raw material, through removing the peel, drying, precrushing, ball milling, centrifugation, washing, after drying process locate in advance The reed rod powder of reason；(2) 1 is pressed:1~3:1~3:1~4 mass ratio, which is weighed, takes reed rod powder, nitrogenous fertilizer, boron fertilizer, potassium hydroxide, after being well mixed Appropriate amount of deionized water is added into system, continues to be evenly stirred until pasty state, through 40~60 degrees Celsius of drying；(3) it is transferred in tube furnace, leads to argon gas or nitrogen, 300 are first warming up to the heating rate of 1~5 degrees celsius/minute~ 400 degrees Celsius and be incubated 1~2 hour, then be warming up to 700~800 degrees Celsius and be incubated 1~2 hour；(4) using hydrochloric acid solution, ethanol and deionized water alternately washing 3 times of 3~8% mass ratioes, to remove remnants reagent, Nitrogen, boron doping porous charcoal are produced after being dried in 40~60 degrees Celsius.
- The preparation method of porous charcoal 5. nitrogen, boron as claimed in claim 4 for electrode of super capacitor adulterates, its feature exists In in step (1), using tissue mashing machine's progress precrushing, planetary ball mill carries out ball-milling treatment, and rotational speed of ball-mill is 400 ~500 revs/min, Ball-milling Time is 12~24 hours, slurry after ball milling again through 3000~5000 revs/min of rotating speed from The heart, sediment is alternately and repeatedly washed 3 times through deionized water and absolute ethyl alcohol, and the reed that must be pre-processed is dried in 40~60 degrees Celsius Bar powder.
- The preparation method of porous charcoal 6. nitrogen, the boron described in claim 1 for electrode of super capacitor adulterate, it is characterised in that Comprise the following steps：(1) the fresh and alive reed containing coring is dug, is mixed in the boron fertilizer of the nitrogenous fertilizer containing 2~5% mass ratioes and 2~5% mass ratioes Cultivated 7~30 days in solution；(2) reed rod of interception step (1) culture, through removing the peel, drying, precrushing, ball milling, centrifugation, washing, after drying process The reed rod powder of nitrating, boron；(3) 1 is pressed:1~4 mass ratio weighs the reed rod powder and potassium hydroxide of nitrating, boron, blended, drying；It is transferred to tubular type In stove, lead to argon gas or nitrogen, 300~400 degrees Celsius and insulation 1~2 are first warming up to the heating rate of 1~5 degrees celsius/minute Hour, then be warming up to 700~800 degrees Celsius and be incubated 1~2 hour；(4) using hydrochloric acid solution, ethanol and deionized water alternately washing 3 times of 3~8% mass ratioes, to remove remnants reagent, Nitrogen, boron doping porous charcoal are produced after being dried in 40~60 degrees Celsius.
- 7. nitrogen that is described in claim 1 or being obtained by any one of claim 2~6 preparation method, boron doping are porous Charcoal as electrode material for super capacitor application.
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