CN105575673A - Preparation method of nitrogen and oxygen in-situ doped porous carbon electrode material and application thereof - Google Patents
Preparation method of nitrogen and oxygen in-situ doped porous carbon electrode material and application thereof Download PDFInfo
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- CN105575673A CN105575673A CN201610139348.8A CN201610139348A CN105575673A CN 105575673 A CN105575673 A CN 105575673A CN 201610139348 A CN201610139348 A CN 201610139348A CN 105575673 A CN105575673 A CN 105575673A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 16
- 239000001301 oxygen Substances 0.000 title claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 7
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 241001465754 Metazoa Species 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 102000008186 Collagen Human genes 0.000 claims abstract description 5
- 108010035532 Collagen Proteins 0.000 claims abstract description 5
- 230000008859 change Effects 0.000 claims abstract description 5
- 229920001436 collagen Polymers 0.000 claims abstract description 5
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 5
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 5
- 239000007833 carbon precursor Substances 0.000 claims abstract description 4
- 239000013078 crystal Substances 0.000 claims abstract description 4
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 25
- 239000003990 capacitor Substances 0.000 claims description 23
- 239000003610 charcoal Substances 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000004080 punching Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 241001494479 Pecora Species 0.000 claims description 3
- 229940036811 bone meal Drugs 0.000 claims description 3
- 239000002374 bone meal Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 241000283707 Capra Species 0.000 abstract 1
- 241000282898 Sus scrofa Species 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 19
- 239000003575 carbonaceous material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- 230000004913 activation Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
The invention relates to a preparation method of nitrogen and oxygen in-situ codoped porous carbon electrode material and an application thereof. The nitrogen and oxygen in-situ codoped porous carbon electrode material is excellent in conductivity, great in chemical stability, three-dimensional and abundant in pore channels. An animal bone, such as an ox bone, a swine bone and a goat bone, is adopted to act as a carbon precursor. The organic component of collagen in the bone acts as a carbon and nitrogen source, and the inorganic component acts as a natural template to act as supporting material in the carbonization process and a pore channel regulating structure for controlling change and size of hydroxyapatite crystals so that the material is prepared. The porous carbon electrode material is abundant and prosperous in pore structures and has micropores, mesopores and macropores with the specific surface of being 1000-3000m<2>g<-1> so that the porous carbon electrode material can be used as supercapacitor electrode material.
Description
Technical field
The invention belongs to electrochemical energy storage field, the preparation method in particular to a kind of nitrogen oxygen original position codope porous carbon material and the application as electrode material for super capacitor.
Background technology
The energy to be depended on for existence and development the most basic power support as the new century mankind.But along with the exhaustion of fossil fuel and the aggravation of environmental pollution, advanced Conversion of Energy and storing technology are that the world today needs badly and solves one of a few hang-up, how in the common issue that future development continuable new forms of energy of green are faced by the current whole world.Along with discovery and the utilization of more new forms of energy such as solar energy, wind energy, tidal energy, biomass energy etc., people need a kind of energy storage devices store and change these energy.In numerous energy storage device, battery and ultracapacitor be two kinds the most frequently used be also that there is most the selection widely using value.Battery has larger energy density, can meet the application demand of most of electronic device, but, chemical cell produces faraday's Charger transfer by electricity and stores electric charge, chemical reaction occurs causes its efficiency for charge-discharge undesirable, and useful life is not long, and temperature influence is larger.Ultracapacitor, also known as electrochemical capacitor, ultracapacitor has possessed the advantage of traditional capacitor and chemical power source, as high energy density, high power density, long cycle life and the characteristic such as environmentally friendly, make it there has been good application on high-power energy conversion, portable electronic device, micro-electrical current equipment.
Active carbon due to its high specific area and relative low cost be the most widely used electrode active material material of electrochemical capacitor.But absorbent charcoal material also exists the not high problem of specific surface utilance, have a strong impact on its performance in super capacitor energy density.At present, be that carbonized stock prepares various structure excellence with biomass, high-ratio surface, introduce the electrode material that a certain amount of heteroatomic porous carbon material becomes a kind of desirable ultracapacitor simultaneously.Electrode material is the important component part of electrochemical capacitor, desirable electrode material design principle: there is flourishing specific area, reasonably hierarchical porous structure and pore-size distribution, good conductivity and wettability, for porous carbon electrode material, the conductivity of the size in hole, shape, distribution, surface nature and material affects the performance of capacitor all widely.Therefore, electrode material is the key factor determining electrochemical capacitor characteristic, and the electrode material of electrochemical capacitor mainly contains two large classes: a class is double layer electrodes material, and a class is fake capacitance electrode material.Therefore, the porous carbon material studying invention high-energy density super capacitor nitrogen oxygen original position codope has very important significance.
Summary of the invention
In order to solve problems of the prior art, the invention provides that a kind of excellent electric conductivity, chemical stability are good, the porous carbon electrode material of nitrogen oxygen original position codope that 3 D stereo, duct are enriched, adopt animal bone, as ox bone, pig bone, sheep bone, as carbon precursor, organic principle collagen in bone as carbon nitrogen source, inorganic constituents as native template, in carbonisation as backing material and control hydroxyapatite crystal change and size control pore passage structure obtained.Described porous carbon electrode material pore structure is abundant flourishing, containing micropore, mesoporous, macropore, and specific surface 1000 ~ 3000m
2g
-1, wherein macropore stores the electrolyte of ultracapacitor as large space, the mass transfer path of mesoporous shortening electrolyte, and micropore is rich in avtive spot, promote to promote charge capacity, simultaneously in-situ doped nitrogen element and oxygen element, the content 0 ~ 8% of nitrogen, the content 5% ~ 20% of oxygen.
Animal bone such as inorganic constituents hydroxyapatite in ox bone etc. is dispersed in the organic substance of collagen in order based on nanoscale, there is exquisite orderly classification layered nano-structure and composition sequence, thus as natural inorganic template, change and size control pore passage structure as backing material and control hydroxyapatite crystal in carbonisation; Wherein collagen is that phosphorus content is high as the feature of carbon source, and is rich in hydroxyl, carboxyl, amino groups, realizes the in-situ doped of nitrogen oxygen by regulation and control carbonisation; In ox bone carbonisation, adopt high-temperature activation carbonization method, by controlling the ratio of activator and carbonized product, the pore structure of regulation and control porous charcoal, is conducive to the formation of three-dimensional hierarchical porous structure, increasing specific surface area.In different electrolytes, carry out electro-chemical test sign by three-electrode system, two electrode systems, the porous carbon material of prepared Heteroatom doping has high ratio capacitance, reversible discharge and recharge, excellent coulombic efficiency and charge and discharge cycles stability.Carry out the assembling of two electrode symmetric capacitors, obtain high energy density and power density in neutral electrolyte, the cycle charge-discharge ultracapacitor electric capacity attenuation rate of up to ten thousand times is very low.
The invention provides the preparation method of the porous carbon electrode material of above-mentioned nitrogen oxygen original position codope, specifically comprise the following steps:
(1) after the clean animal bone cleaned being broken into bone meal, in 300 ~ 500 under inert gas shielding
ocarry out carbonization under C, obtain pre-carbonized product;
(2) by above-mentioned pre-carbonized product and activator ground and mixed evenly after, in 600 ~ 1200 under inert gas shielding
ounder C, carbonization obtains carbonized product again, and wherein the ratio of pre-carbonized product and activator is 1:0.2 ~ 1:3;
(3), after above-mentioned cooled carbonized product being carried out pickling, washing, suction filtration drying, the porous charcoal of Heteroatom doping is obtained.
In a preferred embodiment of the present invention, animal bone is selected from one or more in ox bone, pig bone, sheep bone, is more preferably ox bone.
In a preferred embodiment of the present invention, the heating rate of step (1) and the middle carbonization of step (2) is 1 ~ 7.5
ocmin
-1, temperature retention time is 1 ~ 3h, and described inert gas is by the mixed atmosphere of high pure nitrogen or high-purity argon gas atmosphere or above-mentioned two kinds of high-purity gas.
In a preferred embodiment of the present invention, step (3) is specially and is placed in inorganic acid solution stirring and pickling 8 ~ 15h, after then warm water washing, drying, obtain porous charcoal, described inorganic acid is nitric acid or hydrochloric acid, and described inorganic acid solution concentration is 1 ~ 3M, and baking temperature is 80 ~ 120
oc, drying time is 4 ~ 24h.
In a preferred embodiment of the present invention, described activator is potassium hydroxide.
The present invention also protects the application of porous carbon electrode material as electrode material for super capacitor of above-mentioned nitrogen oxygen original position codope.
The present invention also protects a kind of preparation method of porous carbon electrode of nitrogen oxygen original position codope; porous carbon material obtained above and conductive agent, binding agent being mixed by the mass ratio of 80:10:10 is scattered in absolute ethyl alcohol; ultrasonic 1 ~ 3h; continuous agitation grinding; until gluey; then evenly roll into a slice, be washed into the shape 1 ~ 2cm of regular shape with sheet-punching machine
2, 100 ~ 120 DEG C of drying 12 ~ 24h in an oven, are then pasted onto on nickel foam collector, obtain, wherein active material load capacity 3 ~ 10mgcm at 5 ~ 15MPa pressure, 30 ~ 60s
-2.
Compared with prior art, the present invention has the following advantages:
1, large ratio capacitance.The present invention creatively introduces natural organic/inorganic composite material---and animal bone especially ox bone, as carbon precursor, prepares high surface by pre-carbonization, activation carbonization, the nitrogenous of three-dimensional hierarchical porous structure contains oxygen porous charcoal; There is large electric double layer capacitance, the nitrogen, the oxygen atom that mix at preparation process situ simultaneously, oxygen, nitrogen-atoms promote the wetability of electrode material greatly, increase the utilance of micropore, surface functional group promotes that redox reaction occurs at interface, provides considerable fake capacitance, makes material list reveal splendid charge capacity, higher energy density, can also ensure the high power density properties of the intrinsic of ultracapacitor, the overall ratio capacitance being obtained material by charge-discharge test reaches 435Fg simultaneously
-1.
2, excellent mass-transfer performance, efficiency for charge-discharge, less time constant.By native template and activation regulation and control aperture, duct and specific surface (specific area can be controlled in 1000 ~ 3000m
2g
-1), content of heteroatoms (5% ~ 25%) is is effectively regulated and controled by preparation temperature, activator levels, obtain macropore, three-dimensional porous structure material that mesoporous, micropore is interconnected, wherein macropore stores the electrolyte of ultracapacitor as adequate space, the mass transfer path of mesoporous shortening electrolyte, and micropore is rich in avtive spot, as redox reaction avtive spot, promote to promote electric charge reserves.Hetero-atom oxygen nitrogen promotes the wetability of electrode material greatly, increases the utilance of micropore.
3, high energy density and power density.Adopt porous carbon material prepared by the method for the invention, specific surface is larger and controlled, and surface functional group enriches, and be conducive to reinforcing material wettability of the surface, mix atom N, the load transfer performance improving electrolyte ion also improves the electric conductivity of material.Adopt neutral electrolyte Na
2sO
4, carry out the assembling of symmetric capacitor, obtain very high energy density (41.1Whkg
-1, the gross mass based on the active material of whole capacitor two electrodes), and achieve high power density 29kWkg
-1under, energy density still remains 14.5Whkg
-1.
4, excellent charge and discharge cycles stability.The present invention carries out the cycle charge discharge electrical testing of 20000 times to the symmetrical ultracapacitor assembled, and shows highly stable, and relative to ratio capacitance first, the ratio capacitance conservation rate after 20000 times is up to 95.8%.
5, presoma is discarded animal tissue's organ, is commonly easy to get, with low cost, environmental friendliness, and preparation process is easy to control, simple to operate, is easy to batch production, reaches the object turned waste into wealth, add the Economic Value Added of animal bone.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described:
Fig. 1 is pore size distribution curve and the isothermal nitrogen adsorption desorption curve (illustration) of the porous charcoal of preparation in the embodiment of the present invention 1;
Fig. 2 is the microscopic appearance scanning electron microscope (SEM) photograph of the porous carbon material of the nitrogen oxygen codope of preparation in the embodiment of the present invention 2;
Fig. 3 is surface composition N, O atom XPS spectrum figure of the porous carbon material of the nitrogen oxygen codope of preparation in the embodiment of the present invention 2;
Fig. 4 is the cyclic voltammogram (electrolyte is 6MKOH) of the porous charcoal based super capacitor electrode material of the nitrogen oxygen codope of preparation in the embodiment of the present invention 4,5,6;
Fig. 5 is the ratio capacitance of porous charcoal based super capacitor electrode material and the graph of a relation (electrolyte is 6MKOH) of sweep speed of the nitrogen oxygen codope of preparation in the embodiment of the present invention 4,5,6;
Fig. 6 is the constant current charge-discharge figure (electrolyte is 6MKOH) of the symmetrical ultracapacitor that the porous charcoal of nitrogen oxygen codope in the embodiment of the present invention 7 is assembled as electrode material;
Fig. 7 is that (electrolyte is 1MNa to the cyclic voltammogram of symmetrical ultracapacitor under different scanning rates assembled as electrode material of the porous charcoal of nitrogen oxygen codope in the embodiment of the present invention 7
2sO
4);
Fig. 8 be the symmetrical ultracapacitor assembled as electrode material of the porous charcoal of nitrogen oxygen codope in the embodiment of the present invention 7 under different current density constant current charge-discharge figure (electrolyte is 1MNa
2sO
4);
Fig. 9 be the symmetrical ultracapacitor that the porous charcoal of nitrogen oxygen codope in the embodiment of the present invention 7 is assembled as electrode material energy density and saturation effect figure---Ragon schemes, and (electrolyte is 1MNa
2sO
4);
Figure 10 is that (electrolyte is 1MNa to symmetrical ultracapacitor 20000 cycle charge-discharge ratio capacitance conservation rate figure of assembling as electrode material of the porous charcoal of nitrogen oxygen codope in the embodiment of the present invention 7
2sO
4).
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with specific embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and be not construed as limiting the invention.
Embodiment 1
Clean clean by ox bone, be ground into bone meal and be placed in baking oven and dry, then placing in tube furnace, is 200mLmin at flow
-1high-purity argon gas protection under, with 5
oCmin
-1be warming up to 400
oc carbonization, stops heating after insulation 3h, naturally cools to room temperature, obtain pre-carbonized product; Take the pre-carbonized product of 5g and put into tube furnace, with 2.5 under argon shield with activator KOH by 1:1 quality is more even than ground and mixed
oCmin
-1be warming up to 750
oc, naturally cools to room temperature after insulation 1h, obtains activating carbonized product; Then above-mentioned activation carbonized product is placed in 2molL
-1hNO
3in solution, stirring and pickling 12h, then spends deionized water, and 110
oafter the dry 12h of C, obtain the porous carbon material CB-HPC-750 of nitrogen oxygen codope, hole presents three-dimensional honeycomb network configuration, comprises macropore, mesoporous, micropore, is tested by isothermal nitrogen adsorption desorption, and the specific area adopting BET matching to obtain porous charcoal reaches 1754m
2g
-1, Fig. 1 is shown in by nitrogen adsorption desorption curve and pore-size distribution; Adopting x-ray photoelectron power spectrum to record its oxygen content is 15.7wt%, and nitrogen content is 2.09wt%.
Embodiment 2
Pre-charing adopts the preparation process of embodiment 1, takes the pre-carbonized product of 5g and puts into tube furnace, with 2.5 under argon shield with activator KOH by 1:1 quality is more even than ground and mixed
oCmin
-1be warming up to 850
oc, naturally cools to room temperature after insulation 1h, obtains activating carbonized product; Then above-mentioned activation carbonized product is placed in 2molL
-1hNO
3in solution, stirring and pickling 12h, then spends deionized water, and 110
oafter the dry 12h of C, obtain the porous carbon material CB-HPC-850 of nitrogen oxygen codope, this material hole presents three-dimensional honeycomb network configuration, comprise macropore, mesoporous, micropore, ESEM, as Fig. 2, is tested by isothermal nitrogen adsorption desorption, and the specific area adopting BET matching to obtain porous charcoal reaches 2520m
2g
-1; Adopting x-ray photoelectron power spectrum to record its oxygen content is 10.2wt%, nitrogen content be 1.56wt%, XPS entirely compose and N, O High Resolution Spectrum as Fig. 3.
Embodiment 3
Pre-charing adopts the preparation process of embodiment 1, takes the pre-carbonized product of 5g and puts into tube furnace, with 2.5 under argon shield with activator KOH by 1:1 quality is more even than ground and mixed
oCmin
-1be warming up to 950
oc, naturally cools to room temperature after insulation 1h, obtains activating carbonized product; Then above-mentioned activation carbonized product is placed in 2molL
-1hNO
3in solution, stirring and pickling 12h, then spends deionized water, and 110
oafter the dry 12h of C, obtain the porous carbon material CB-HPC-950 of nitrogen oxygen codope, tested by isothermal nitrogen adsorption desorption, the specific area adopting BET matching to obtain porous charcoal reaches 1123m
2g
-1; Adopting x-ray photoelectron power spectrum to record its oxygen content is 9.2wt%, and nitrogen content is 1.01wt%.
Embodiment 4
Step one: specific area is reached 1754m
2g
-1, the porous carbon material CB-HPC-750 of oxygen content 15.7wt%, nitrogen content 2.09wt% and conductive agent and binding agent mix in the ratio of 80:10:10 and are scattered in absolute ethyl alcohol, ultrasonic 1h, continuous agitation grinding, until gluey, then evenly rolls into a slice, the circle of regular shape is washed into sheet-punching machine, 100 DEG C of dry 12h in an oven, are then pasted onto on nickel foam collector, more suitably at 15MPa pressure 30s, obtain electrode to be tested, active material load capacity 4mgcm
-2left and right.
Step 2: with the electrode of preparation in step one for work electrode, platinized platinum is to electrode, and SCE is that reference electrode is assembled into three-electrode system, carries out electrochemical property test, and 6MKOH is electrolyte.As Fig. 4, the CV curve of 5, CB-HPC-750 presents deformation rectangle profile, and ratio capacitance is electric double layer capacitance and fake capacitance joint contribution, is 5mVs in sweep speed
-1under be 400Fg by calculating the ratio capacitance of CB-HPC-750 Carbon Materials
-1.
Embodiment 5
Step one: specific area is reached 2520m
2g
-1, the porous carbon material CB-HPC-850 of oxygen content 10.2wt%, nitrogen content 1.56wt% and conductive agent and binding agent mix in the ratio of 80:10:10 and are scattered in absolute ethyl alcohol, ultrasonic 2h, continuous agitation grinding, until gluey, then rolls uniformly a slice, the circle of regular shape is washed into sheet-punching machine, 100 DEG C of dry 12h in an oven, are then pasted onto on nickel foam collector, more suitably at 15MPa pressure 30s, obtain electrode to be tested, active material load capacity 4mgcm
-2left and right.
Step 2: with the electrode of preparation in step one for work electrode, platinized platinum is to electrode, and SCE is that reference electrode is assembled into three-electrode system, carries out electrochemical property test, and 6MKOH is electrolyte.As Fig. 4, the CV curve of 5, CB-HPC-850 presents the rectangular profile of distortion equally, and ratio capacitance comprises electric double layer capacitance and fake capacitance, and is 5mVs in sweep speed
-1under calculate CB-HPC-850 Carbon Materials ratio capacitance be 414Fg
-1.In figure 6, carried out constant current charge-discharge test again to CB-HPC-850 material, can find, CLB reveals symmetrical triangle, describes excellent reversibility and coulombic efficiency.And be 0.1Ag in current density
-1under the ratio capacitance that obtains be 435Fg
-1, this and CV test result are substantially identical.
Embodiment 6
Step one: specific area is reached 1123m
2g
-1, the porous carbon material CB-HPC-950 of oxygen content 9.2wt%, nitrogen content 1.01wt% and conductive agent and binding agent mix in the ratio of 80:10:10 and are scattered in absolute ethyl alcohol, ultrasonic 2h, continuous agitation grinding, until gluey, then rolls uniformly a slice, the circle of regular shape is washed into sheet-punching machine, 100 DEG C of dry 12h in an oven, are then pasted onto on nickel foam collector, more suitably at 15MPa pressure 30s, obtain electrode to be tested, active material load capacity 4mgcm
-2left and right.
Step 2: with the electrode of preparation in step one for work electrode, platinized platinum is to electrode, and SCE is that reference electrode is assembled into three-electrode system, carries out electrochemical property test, and 6MKOH is electrolyte.CV curve as Fig. 4, CB-HPC-950 presents the profile closest to rectangle equally, and the minimum ratio capacitance major embodiment of CB-HPC-950 material content of heteroatoms is electric double layer capacitance.Be 5mVs in sweep speed
-1under calculate CB-HPC-950 Carbon Materials ratio capacitance be 250Fg
-1, as shown in Figure 5.
Embodiment 7
Step one: specific area is reached 2520m
2g
-1, the porous carbon material CB-HPC-850 of oxygen content 10.2wt%, nitrogen content 1.56wt% and conductive agent and binding agent mix in the ratio of 80:10:10 and are scattered in absolute ethyl alcohol, ultrasonic 2h, continuous agitation grinding, until gluey, then rolls uniformly a slice, the circle of regular shape is washed into sheet-punching machine, 100 DEG C of dry 12h in an oven, are then pasted onto on nickel foam collector, more suitably at 15MPa pressure 30s, obtain electrode to be tested, active material load capacity 4mgcm
-2left and right.
Step 2: with the electrode that the load material of preparation in step one is equal or close, centre barrier film separates, and is assembled into two symmetrical electrode systems, carries out electrochemical property test, 1MNa
2sO
4for electrolyte.To the symmetric capacitor assembled voltage window be 1.8V carried out CV, GCD test, as Fig. 7,8, under different sweep speeds, CV test curve shows the profile of perfect rectangle, when sweep speed increases to 2000mVs
-1time, shape only has distortion a little, reflects the high rate performance of capacitor excellence.The ratio capacitance that constant current charge-discharge measuring and calculation obtains symmetric capacitor is 91.6Fg
-1.Through calculating specific energy and the specific power graph of a relation 9 of capacitor.The energy density of this capacitor can reach 41.1Whkg
-1(gross mass based on the active material of whole capacitor two electrodes), and achieve high power density 29kWkg
-1under, energy density still remains 14.5Whkg
-1.As Figure 10, the symmetrical ultracapacitor assembled is carried out to the cycle charge discharge electrical testing of 20000 times, show highly stable, compare ratio capacitance first, the ratio capacitance conservation rate after 20000 times is up to 95.8%.
Above embodiment display and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification just illustrates principle of the present invention; instead of limit the scope of the invention by any way; without departing from the scope of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in claimed scope.
Claims (8)
1. the porous carbon electrode material of a nitrogen oxygen original position codope, it is characterized in that, adopt animal bone as carbon precursor, organic principle collagen in bone is as carbon nitrogen source, inorganic constituents as native template, as backing material and control hydroxyapatite crystal change and size control pore passage structure obtains, the abundant prosperity of described porous carbon electrode material pore structure in carbonisation, containing micropore, mesoporous, macropore, specific surface 1000 ~ 3000m
2g
-1, simultaneously in-situ doped nitrogen element and oxygen element, the content 0 ~ 8% of nitrogen, the content 5% ~ 20% of oxygen.
2. a preparation method for the porous carbon electrode material of nitrogen oxygen original position codope, is characterized in that, comprise the steps:
(1) after the clean animal bone cleaned being broken into bone meal, in 300 ~ 500 under inert gas shielding
ocarry out carbonization under C, obtain pre-carbonized product;
(2) by above-mentioned pre-carbonized product and activator ground and mixed evenly after, in 600 ~ 1200 under inert gas shielding
ounder C, carbonization obtains carbonized product again, and wherein the ratio of pre-carbonized product and activator is 1:0.2 ~ 1:3;
(3), after above-mentioned cooled carbonized product being carried out pickling, washing, suction filtration drying, the porous charcoal of Heteroatom doping is obtained.
3. preparation method according to claim 2, is characterized in that, described animal bone is selected from one or more in ox bone, pig bone, sheep bone, is more preferably ox bone.
4. preparation method according to claim 2, is characterized in that, the heating rate of step (1) and the middle carbonization of step (2) is 1 ~ 7.5
ocmin
-1, temperature retention time is 1 ~ 3h, and described inert gas is by the mixed atmosphere of high pure nitrogen or high-purity argon gas atmosphere or above-mentioned two kinds of high-purity gas.
5. preparation method according to claim 2, it is characterized in that, step (3) is specially and is placed in inorganic acid solution stirring and pickling 8 ~ 15h, then after warm water washing, drying, obtain porous charcoal, described inorganic acid is nitric acid or hydrochloric acid, and described inorganic acid solution concentration is 1 ~ 3M, and baking temperature is 80 ~ 120
oc, drying time is 4 ~ 24h.
6. preparation method according to claim 2, is characterized in that, described activator is potassium hydroxide.
7. the porous carbon electrode material of the nitrogen oxygen original position codope described in claim 1-6 is as the application of electrode material for super capacitor.
8. the preparation method of the porous carbon electrode of a nitrogen oxygen original position codope, it is characterized in that, the porous carbon electrode material of the nitrogen oxygen original position codope described in claim 1-6 and conductive agent, binding agent being mixed by the mass ratio of 80:10:10 is scattered in absolute ethyl alcohol, ultrasonic 1 ~ 3h, continuous agitation grinding, until gluey, then evenly roll into a slice, be washed into the shape 1 ~ 2cm of regular shape with sheet-punching machine
2, 100 ~ 120 DEG C of drying 12 ~ 24h in an oven, are then pasted onto on nickel foam collector, obtain, wherein active material load capacity 3 ~ 10mgcm at 5 ~ 15MPa pressure, 30 ~ 60s
-2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993068A (en) * | 2010-10-27 | 2011-03-30 | 北京化工大学 | Preparation method of porous structured active carbon |
| CN105152170A (en) * | 2015-10-13 | 2015-12-16 | 东南大学 | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor |
-
2016
- 2016-03-11 CN CN201610139348.8A patent/CN105575673B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993068A (en) * | 2010-10-27 | 2011-03-30 | 北京化工大学 | Preparation method of porous structured active carbon |
| CN105152170A (en) * | 2015-10-13 | 2015-12-16 | 东南大学 | Preparation method for cicada slough based porous carbon material used for electrochemical capacitor |
Non-Patent Citations (2)
| Title |
|---|
| MEILING DOU, ET AL.: ""Pyrolysis of Animal Bones with Vitamin B12: A Facile Route to Efficient Transition Metal–Nitrogen–Carbon (TM-N-C) Electrocatalysts for Oxygen Reduction"", 《CHEM. EUR. J.》 * |
| WENTAO HUANG, ET AL.: ""Hierarchical porous carbon obtained from animal bone and evaluation in electric double-layer capacitors"", 《CARBON》 * |
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