CN106185920A - A kind of porous carbon materials and its preparation method and application - Google Patents
A kind of porous carbon materials and its preparation method and application Download PDFInfo
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- CN106185920A CN106185920A CN201610492629.1A CN201610492629A CN106185920A CN 106185920 A CN106185920 A CN 106185920A CN 201610492629 A CN201610492629 A CN 201610492629A CN 106185920 A CN106185920 A CN 106185920A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000003763 carbonization Methods 0.000 claims abstract description 29
- 230000004913 activation Effects 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 26
- 239000008247 solid mixture Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002699 waste material Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 12
- 229920005610 lignin Polymers 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000012190 activator Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 238000001994 activation Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- 239000000843 powder Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000002994 raw material Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000006260 foam Substances 0.000 description 13
- 229910052759 nickel Inorganic materials 0.000 description 13
- 239000003990 capacitor Substances 0.000 description 11
- 238000012546 transfer Methods 0.000 description 10
- 239000006258 conductive agent Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000010902 straw Substances 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000006213 oxygenation reaction Methods 0.000 description 7
- 238000004088 simulation Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000006071 cream Substances 0.000 description 6
- 229910052738 indium Inorganic materials 0.000 description 6
- 229950000845 politef Drugs 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- -1 oxo phenylpropanol Chemical compound 0.000 description 1
- 229950009195 phenylpropanol Drugs 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000010025 steaming Methods 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
-
- 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
-
- 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
-
- 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)
- Carbon And Carbon Compounds (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention provides a kind of porous carbon materials and its preparation method and application.The present invention is with the lignin in the black liquid that the alkali paper-making containing KOH produces as carbon source, preprocessed, carbonization and activation, during described activation, KOH in black liquid plays the effect of activator, obtaining the porous carbon materials with high-specific surface area, specific surface area is 1500～3000m2/ g, pore-size distribution is 0.5～3nm, based on micropore (50～80%), mesopore (20～50%) is auxiliary, the ultracapacitor assembled as electrode material has good chemical property and cycle performance, than electric capacity up to 337F/g, after 3000 times circulate, electric capacity is maintained at more than 98%.The preparation method that the present invention provides is simple to operate, mild condition, energy consumption are low, with low cost, technique is easily-controllable, and suitable large-scale industry is promoted.
Description
Technical field
The present invention relates to technical field of function materials, particularly to a kind of porous carbon materials and its preparation method and application.
Background technology
Ultracapacitor is also known as electrochemical capacitor, has the spies such as fast charging and discharging, power density is big, have extended cycle life
Point.Performances based on these excellences, ultracapacitor can be as free of contamination back-up source for multiple electric equipment, simultaneously
It also can collectively constitute composite power source with battery and provide power for electric automobile, receives significant attention in recent years and is quickly sent out
Exhibition.
Ultracapacitor is different from traditional electrochmical power source, be a kind of between traditional capacitor and battery, there is spy
The power supply of different performance, relies primarily on electric double layer and oxidoreduction fake capacitance electric charge stores electric energy, but its energy storage process not
Chemical reaction occurs, and this thermal energy storage process is reversible.Its ultimate principle is the same with the double layer capacitor of other kind, is all
The double electrical layers utilizing activated carbon porous electrode and electrolyte composition obtains the capacity of super large.
In the prior art, use starch, polymer etc. to prepare porous carbon materials as carbon source more.In generation, inspires and reports one
Plant the method preparing porous carbon materials for carbon source with starch, (in generation, inspires. the research of porous carbon materials is prepared with starch for presoma
[D]. Guangxi Normal University, 2008.)；The Chinese patent of Publication No. CN104086678A discloses a kind of polymer carbon material
The preparation method of material, and specifically disclose with alkali metal or alkaline-earth metal and polyalkenyl halides, halogenated polyolefin, polyhalohydrocarbon or
Its derivant is that raw material prepares porous carbon materials.But the cost of material of said method is higher, and preparation method is complicated.
The steaming and decocting in paper mill now commonly uses chemical drugs dissolution, the course of reaction of removing lignin, by the lignin of Caulis et Folium Oryzae
It is degraded into low molecule lignin, the dissolution adding lignin and the ability extracted, thus realize lignin and cellulose, hemicellulose
Separation.Some waste liquids can be produced during using oxygenation pretreatment and be pretreated black liquor.Under normal circumstances, black liquor is straight
Run in into sewage treatment plant, so can be greatly increased the expenses of environmental protection of sewage disposal.
Summary of the invention
It is an object of the invention to provide a kind of porous carbon materials and its preparation method and application.The preparation that the present invention provides
Method is with low cost, and the porous carbon materials of preparation has big specific surface area, can be used for preparing and has good electrical chemical property
Ultracapacitor.
The invention provides the preparation method of a kind of porous carbon materials, comprise the following steps:
(1) black liquid being carried out pretreatment, obtain solid mixture, described black liquid is containing of alkali paper-making generation
There is the waste liquid of KOH；
(2) solid mixture that described step (1) obtains is carried out carbonization, obtain material with carbon element；
(3) material with carbon element that described step (2) obtains is activated, obtain porous carbon materials.
Preferably, described in step (1), black liquid mixes with tripolycyanamide before pretreatment, obtains mixed solution.
Preferably, the quality of described tripolycyanamide is the 0.5～2% of black liquid quality.
Preferably, in described step (2), carbonization is carried out under inert gas shielding.
Preferably, the temperature of described carbonization is 350～450 DEG C, and the time of carbonization is 0.5～1.5h.
Preferably, in described step (3), activation is carried out under inert gas shielding.
Preferably, the temperature of described activation is 600～900 DEG C, and the time of activation is 0.5～1.5h.
Present invention also offers porous carbon materials prepared by preparation method described in technique scheme, described porous carbon materials
Specific surface area be 1500～3000m2/g。
Preferably, the aperture of described porous carbon materials is 0.5～3nm.
Present invention also offers the application in ultracapacitor of the porous carbon materials described in technique scheme.
The present invention with containing KOH alkali paper-making produce black liquid in lignin as carbon source, preprocessed, carbonization
And activation, during described activation, the KOH in black liquid plays the effect of activator, obtains having high-specific surface area
Porous carbon materials.Test result indicate that, the specific surface area of porous carbon materials prepared by the preparation method that the present invention provides is
1500～3000m2/ g, pore-size distribution is 0.5～3nm, and based on micropore (50～80%), mesopore (20～50%) is auxiliary, makees
The ultracapacitor assembled for electrode material has good chemical property and cycle performance, than electric capacity up to 337F/g,
After 3000 circulations, electric capacity is maintained at more than 98%.
The preparation method that the present invention provides is simple to operate, mild condition, energy consumption are low, with low cost, technique is easily-controllable, the most greatly
Technical scale is promoted.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the porous carbon materials obtained in embodiment 7；
Fig. 2 is the graph of pore diameter distribution of the porous carbon materials obtained in embodiment 7；
Fig. 3 is the SEM figure of the porous carbon materials obtained in embodiment 9；
Fig. 4 is the graph of pore diameter distribution of the porous carbon materials obtained in embodiment 9；
Fig. 5 is the cyclic voltammetry curve of the carbon electrode obtained in embodiment 10；
Fig. 6 is the constant current charge-discharge curve of the carbon electrode obtained in embodiment 10；
Fig. 7 is the SEM figure of the porous carbon materials obtained in embodiment 11；
Fig. 8 is the graph of pore diameter distribution of the porous carbon materials obtained in embodiment 11.
Detailed description of the invention
The invention provides the preparation method of a kind of porous carbon materials, comprise the following steps:
(1) black liquid being carried out pretreatment, obtain solid mixture, described black liquid is containing of alkali paper-making generation
There is the waste liquid of KOH；
(2) solid mixture that described step (1) obtains is carried out carbonization, obtain material with carbon element；
(3) material with carbon element that described step (2) obtains is activated, obtain porous carbon materials.
The present invention with in black liquid as raw material, described black liquid be alkali paper-making produce the waste liquid containing KOH.
Rich in there being substantial amounts of lignin (Lignin) in black liquid, it is a kind of unbodied, molecule being widely present in plant
Structure contains the armaticity high polymer of oxo phenylpropanol or derivatives thereof construction unit, by obtaining after carbonization and activation
High-quality material with carbon element；KOH in described black liquid is as activator, by reacting with carbon in activation process, generates H2、CO、
CO2Deng gas, effective exploitation goes out mesopore and microcellular structure.
The method that the present invention provides can be with in papermaking enterprise, and the waste liquid that alkali paper-making technique produces is raw material, it is also possible to
Simulation alkali paper-making process, prepares black liquid voluntarily.In the present invention, the preparation of described black liquid preferably includes following step
Rapid:
A fibrous raw material is mixed by () with KOH solution, reaction obtains mixed material；
B mixed material that described step (a) is obtained by () carries out solid-liquid separation, obtains black liquid.
Fibrous raw material is preferably mixed by the present invention with KOH solution, and reaction obtains mixed material.In the present invention, described fibre
Dimension raw material is preferably 1:0.2～0.8, more preferably 1:0.4～0.6 with the mass ratio of KOH.
The present invention does not has special restriction to kind and the source of described fibrous raw material, uses those skilled in the art to know
Papermaking fibers raw material.In the present invention, described fibrous raw material is preferably Plant fiber, more preferably Caulis et Folium Oryzae, Semen Maydis
One or more in straw, wheat straw and timber.
In the present invention, described fibrous raw material carries out pretreatment the most before use, obtains fiber dust.In the present invention
In, described pretreatment includes pulverizing and being dried.The present invention does not has special restriction to the equipment of described pulverizing, uses this area skill
The equipment of the comminuting matter known to art personnel.In the present invention, described pulverizing is preferably carried out in pulverizer；Described pulverizing
The granularity of rear fibrous raw material is preferably not lower than 40 mesh.
Fibrous raw material after the present invention preferably will pulverize is dried process, obtains fiber dust.In the present invention, described
The temperature being dried is preferably 100～110 DEG C, more preferably 103～107 DEG C；The described dry time is preferably 11～13h, more
It is preferably 11.5～12.5h.
In the present invention, described KOH preferably adds with the form of KOH solution, and the mass concentration of described KOH solution is preferably
2～8%, more preferably 4～6%.
The present invention does not has special restriction with KOH solution to the operation that described fibrous raw material mixes, and uses art technology
The technical scheme preparing mixed material known to personnel.In the present invention, described mixing is carried out the most under agitation.
In the present invention, the speed of described stirring is preferably 100～800r/min, more preferably 300～500r/min, most preferably
350～450r/min；The time of described stirring is preferably 2～6min, more preferably 3～5min.
The present invention does not has special restriction to the device of described reaction, uses reaction unit well known to those skilled in the art
?.In the present invention, described reaction is carried out the most in a kettle.；Described reactor is preferably stainless steel cauldron；Described
The liner of reactor is preferably politef.In the present invention, the temperature of described reaction is preferably 110～130 DEG C, more preferably
It is 115～125 DEG C, most preferably 118～122 DEG C；The time of described reaction is preferably 4～6h, more preferably 4.5～5.5h.
In the present invention, in described course of reaction, KOH solution, by the lignin dissolution in fibrous raw material, obtains alkaline mixt material.
Described mixed material is carried out psychrolusia and is cooled to room temperature by the present invention the most after the completion of reaction.In the present invention,
Described cooldown rate is preferably 4～6 DEG C/min.
After described cooling completes, the mixed material that cooling is preferably obtained by the present invention separates, and obtains black liquid.?
In the present invention, described separation is preferably centrifugation；The rotating speed of described centrifugation is preferably 3500～4500r/min, more excellent
Elect 3800～4200r/min as.
After obtaining black liquid, described black liquid is preferably mixed by the present invention with tripolycyanamide, obtains mixed solution.?
In the present invention, the Functionality, quality and appealing design of described tripolycyanamide elects the 0.2～5% of black liquid quality, more preferably 0.5～2% as.At this
In invention, described tripolycyanamide part, as nitrogen source, provides N for porous carbon materials, exists with N-O key-like formula at carbon material surface
, hydrogen bond can be formed in the electrolytic solution so that the electrode material made has good wettability and electric conductivity, thus significantly
Improve capacitive effect；Additionally, high-temperature lower part divides tripolycyanamide to decompose, N can be generated2And salt, salt plays the work of drilling after eluting
With.
The present invention does not has special restriction with tripolycyanamide to the operation that described black liquid mixes, and uses art technology
The operation preparing mixed solution known to personnel.In the present invention, described mixing is carried out the most under agitation；Described
The speed of stirring is preferably 100～800r/min, more preferably 300～500r/min；The time of described stirring be preferably 2～
6min, more preferably 3～5min.
The present invention is the most before carbonization by described black liquid or include that the mixed solution of black liquid and tripolycyanamide enters
Row pretreatment, obtains solid mixture.In the present invention, described pretreatment is preferably and is dried.In the present invention, described dry
Temperature is preferably 80～90 DEG C, more preferably 84～86 DEG C；The described dry time be preferably 10～14h, more preferably 11～
13h。
After completing described pretreatment, the solid mixture obtained is carried out carbonization by the present invention, obtains material with carbon element.The present invention is excellent
Choosing is incubated after described solid mixture is warming up to carburizing temperature, carries out carbonization.In the present invention, the temperature of described carbonization is preferred
It is 350～450 DEG C, more preferably 380～420 DEG C；The time of described carbonization be preferably 0.5～1.5h, more preferably 0.8～
1.2h；Described heating rate is preferably 1.5～2.5 DEG C/min.In the present invention, described carbonization is preferably under inert gas shielding
Carry out；The airflow rate of described noble gas is preferably 0.7～0.9L/min.
After obtaining described material with carbon element, described material with carbon element is activated by the present invention, obtains porous carbon materials.The present invention is preferred
It is incubated after described material with carbon element is warming up to activation temperature, activates.In the present invention, the temperature of described activation is preferably 600
～900 DEG C, more preferably 700～800 DEG C, most preferably 730～760 DEG C；The time of described activation is preferably 0.5～1.5h,
More preferably 0.8～1.2h；Described heating rate is preferably 4～6 DEG C/min.In the present invention, described activation is preferably in inertia
Carry out under gas shield；The airflow rate of described noble gas is preferably 0.7～0.9L/min.In the present invention, described activation
During KOH can effectively develop mesopore and micropore, central hole structure be ion provide diffusion passage, microcellular structure is favourable
In the adsorption desorption of ion, so that porous carbon materials has good capacitive properties.
For improving the purity of porous carbon materials, the porous carbon materials that described activation obtains is washed and does by the present invention
Dry.The present invention does not has special restriction to described washing and dry operation, use washing well known to those skilled in the art and
The technical scheme being dried.In the present invention, the detergent of described washing is preferably distilled water and ethanol.Reality in the present invention
Execute in example, it is preferred to use the alternately washing of distilled water and ethanol；The number of times of described distilled water and washing with alcohol is respectively preferably 2～4
Secondary.In the present invention, described dry temperature is preferably 70～90 DEG C, more preferably 75～85 DEG C；The described dry time is excellent
Elect 11～13h as, more preferably 11.5～12.5h.
Present invention also offers porous carbon materials prepared by preparation method described in technique scheme, described porous carbon materials
Specific surface area be 1500～3000m2/ g, more preferably 1800～2200m2/g.In the present invention, described porous carbon materials
Pore-size distribution is preferably 0.5～3nm, more preferably 1～2nm；In described porous carbon materials the ratio of micropore be preferably 50～
80%, more preferably 60～70%；The ratio of mesopore is preferably 20～50%, more preferably 30～40%.In the present invention, institute
The central hole structure stating porous carbon materials provides the passage of diffusion for ion, and microcellular structure is conducive to the adsorption desorption of ion, applicable
Mesopore, microcellular structure ratio make electrode material have preferable capacitive properties.
In the present invention, according to elementary composition meter, it is 75～90% that described porous carbon materials preferably includes mass fraction
Carbon, 5～the oxygen of 20% and 1～the nitrogen of 6%.In the present invention, described nitrogen and oxygen are distributed in porous carbon materials with N-O key-like formula
Surface, can form hydrogen bond in the electrolytic solution so that the electrode material made has good wettability and electric conductivity, improves electricity
Hold effect.
Present invention also offers the application in ultracapacitor of the above-mentioned porous carbon materials, the most specifically as super capacitor
The application of the carbon electrode of device.
In the present invention, described carbon electrode preferably includes porous carbon materials, conductive agent, binding agent and collector.At this
In bright, the mass ratio of described porous carbon materials, conductive agent and binding agent is preferably (6～10): (0.3～2): (0.3～2), more
It is preferably (7～9): (0.5～1.5): (0.5～1.5).
The present invention does not has special restriction for the kind of described conductive agent, uses conduction well known to those skilled in the art
Agent.In the present invention, described conductive agent is preferably carbon black conductive agent, more preferably specifically includes acetylene black, electrically conductive graphite KS-
6 or Ketjen black.
The present invention does not has special restriction for the kind of described binding agent, uses bonding well known to those skilled in the art
Agent.In the present invention, described binding agent is preferably politef or Kynoar.
The present invention does not has special restriction for described collector, uses collector well known to those skilled in the art i.e.
Can.In the present invention, described collector preferably includes nickel foam.
The present invention does not has special restriction for the preparation method of described carbon electrode, uses well known to those skilled in the art
Prepare the technical scheme of carbon electrode.In the present invention, the preparation method of described carbon electrode preferably includes following steps:
Porous carbon materials is mixed with conductive agent, binding agent and ethanol, obtains mixed material；
Described mixed material is coated on a current collector, is dried to obtain carbon electrode.
Described porous carbon materials is mixed by the present invention with conductive agent, binding agent and ethanol, obtains mixed material.In the present invention
In, described porous carbon materials, conductive agent and binding agent total concentration in ethanol is preferably 0.2～1g/L, more preferably 0.5g/
L。
The mode that porous carbon materials mixes with conductive agent, binding agent, ethanol is not had special limit for described by the present invention
Fixed, use well known to those skilled in the art can be by the technical scheme of raw material mix homogeneously.In the present invention, described mixed
Close and carry out the most under agitation；The speed of described stirring is preferably 300～500r/min；The time of described stirring is preferably
3～5min.
After completing described mixing, the mixed material obtained is coated on a current collector by the present invention, is dried, obtains carbon electrode.
The present invention does not has special restriction for described coating, uses the technical scheme of coating well known to those skilled in the art.
In the present invention, described porous carbon materials load capacity on a current collector is preferably 4～6g/cm2。
After the coating on a current collector of described mixed material, the collector after coating is dried by the present invention, obtains carbon
Electrode.The present invention does not has special restriction for described dry mode, uses dry skill well known to those skilled in the art
Art scheme.In the present invention, described being dried is preferably vacuum drying；Described vacuum drying vacuum be preferably 0.08～
0.12Pa；Described vacuum drying temperature is preferably 40～60 DEG C, more preferably 45～55 DEG C；The described vacuum drying time is excellent
Elect 8～13h as, more preferably 10～11h.
In order to further illustrate the present invention, below in conjunction with the embodiment preparation method to the porous carbon materials that the present invention provides
It is described in detail, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1:
(1) first being dried by Caulis et Folium Oryzae and grind afterwards, then cross the steel sieve of 40 mesh, the Caulis et Folium Oryzae powder obtained is dried at 105 DEG C
12 hours；
(2) using KOH solution that mass concentration is 2% as the alkali liquor of Caulis et Folium Oryzae pretreatment, the rice straw powder that step (1) is obtained
End weighs the KOH solution of 10g with 100mL and mixes；
(3), after being stirred by the mixture in step (2), teflon-lined stainless steel cauldron is transferred to
In, at 120 DEG C, reaction carries out oxygenation pretreatment reaction in 4 hours；
(4) product that obtains in step (3) speed with 5 DEG C/min in psychrolusia is cooled down, with the speed of 4000r/min
Rate is centrifugal draws black liquor, and freeze-day with constant temperature 12h in an oven removes whole moisture, obtains solid mixture；
(5) transfer to, in corundum boat, transfer to afterwards in tube furnace by the solid mixture in step (4), use and heat up
Speed is to keep after 2 DEG C/min rises to 400 DEG C within one hour, carrying out carbonization, is that 5 DEG C/min rises to 800 with heating rate the most again
Keeping after DEG C activating for one hour, carbonization and activation process use nitrogen to protect, and airflow rate is 800mL/min；
(6) reaction is cooled to room temperature after terminating, and the black powder distilled water of generation and ethanol alternately wash each 3 times, then
Removing whole moisture in 80 DEG C of freeze-day with constant temperature 12h, obtain the porous carbon materials in black, specific surface area has reached 1357m2/
g。
Embodiment 2:
By made for embodiment 1 porous carbon materials and acetylene black, politef, ratio for 80:10:10 in mass ratio is entered
Row mixing, adds the even cream of ethanol furnishing, uses nickel foam to do collector, is coated in nickel foam, and at 50 DEG C, vacuum 0.1Pa is dried
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assemble simulation ultracapacitor cell and be circulated volt-ampere and constant current charge and discharge
Electrical testing.
Test shows, after porous carbon materials prepared by the present embodiment makes super capacitor, under three electrode tests, than electricity
Hold and reached 234F/g.
Embodiment 3:
(1) first being dried by Caulis et Folium Oryzae and grind afterwards, then cross the steel sieve of 40 mesh, the Caulis et Folium Oryzae powder obtained is dried at 105 DEG C
12 hours；
(2) using KOH solution that mass concentration is 5% as the alkali liquor of Caulis et Folium Oryzae pretreatment, the rice straw powder that step (1) is obtained
End weighs the KOH solution of 10g with 100mL and mixes；
(3), after being stirred by the mixture in step (2), teflon-lined stainless steel cauldron is transferred to
In, at 120 DEG C, reaction carries out oxygenation pretreatment reaction in 5 hours；
(4) product that obtains in step (3) speed with 5 DEG C/min in psychrolusia is cooled down, with the speed of 4000r/min
Rate is centrifugal draws black liquor, and freeze-day with constant temperature 12h in an oven removes whole moisture, obtains solid mixture；
(5) solid mixture in step (4) is transferred in corundum boat, be that 2 DEG C/min rises to 400 DEG C with heating rate
Rear holding carries out carbonization for one hour, then is to keep after 5 DEG C/min rises to 800 DEG C activating for one hour with heating rate,
Carbonization and activation process use argon to protect, and airflow rate is 800mL/min；
(6) reaction is cooled to room temperature after terminating, and the black powder distilled water of generation and ethanol alternately wash each 3 times, then
Removing whole moisture in 80 DEG C of freeze-day with constant temperature 12h, obtain the porous carbon materials in black, specific surface area has reached 1521m2/
g。
Embodiment 4:
It is the ratio of 80:10:10 in mass ratio by made for embodiment 3 porous carbon material and super P white carbon black, Kynoar
Example mixes, and adds the even cream of ethanol furnishing, uses nickel foam to do collector, is coated in nickel foam, vacuum 0.1Pa at 50 DEG C
It is dried overnight, obtains carbon electrode.
Using the KOH of 6mol/L as electrolyte, assemble simulation ultracapacitor cell and be circulated volt-ampere and constant current charge and discharge
Electrical testing.
Test shows, after porous carbon materials prepared by the present embodiment makes super capacitor, under three electrode tests, than electricity
Hold and reached 242F/g.
Embodiment 5:
(1) first being dried by Caulis et Folium Oryzae and grind afterwards, then cross the steel sieve of 40 mesh, the Caulis et Folium Oryzae powder obtained is dried at 105 DEG C
12 hours；
(2) using KOH solution that mass concentration is 8% as the alkali liquor of Caulis et Folium Oryzae pretreatment, the rice straw powder that step (1) is obtained
End weighs the KOH solution of 10g with 100mL and mixes；
(3), after being stirred by the mixture in step (2), teflon-lined stainless steel cauldron is transferred to
In, at 120 DEG C, reaction carries out oxygenation pretreatment reaction in 6 hours；
(4) product that obtains in step (3) speed with 5 DEG C/min in psychrolusia is cooled down, with the speed of 4000r/min
Rate is centrifugal draws black liquor, and freeze-day with constant temperature 12h in an oven removes whole moisture, obtains solid mixture；
(5) transfer to, in corundum boat, transfer to afterwards in tube furnace by the solid mixture in step (4), with the speed that heats up
Rate is to keep carrying out for one hour carbonization after 2 DEG C/min rises to 400 DEG C, then is to protect after 5 DEG C/min rises to 800 DEG C with heating rate
Holding one hour and activate, carbonization and activation use nitrogen to protect, and airflow rate is 800mL/min；
(6) reaction is cooled to room temperature after terminating, and the black powder distilled water of generation and ethanol alternately wash each 3 times, then
Removing whole moisture in 80 DEG C of freeze-day with constant temperature 12h, obtain the porous carbon materials in black, specific surface area has reached 1230m2/
g。
Embodiment 6:
By made for embodiment 5 porous carbon materials and acetylene black, politef, ratio for 80:10:10 in mass ratio is entered
Row mixing, adds the even cream of ethanol furnishing, uses nickel foam to do collector, is coated in nickel foam, and at 50 DEG C, vacuum 0.1Pa is dried
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assemble simulation ultracapacitor cell and be circulated volt-ampere and constant current charge and discharge
Electrical testing.
Test shows, after porous carbon materials prepared by the present embodiment makes super capacitor, under three electrode tests, than electricity
Hold and reached 169F/g.
Embodiment 7:
(1) first being dried by Caulis et Folium Oryzae and grind afterwards, then cross the steel sieve of 40 mesh, the Caulis et Folium Oryzae powder obtained is dried at 105 DEG C
12 hours；
(2) using KOH solution that mass concentration is 5% as the alkali liquor of Caulis et Folium Oryzae pretreatment, the rice straw powder that step (1) is obtained
End weighs the KOH solution of 10g with 100mL and mixes；
(3), after being stirred by the mixture in step (2), teflon-lined stainless steel cauldron is transferred to
In, at 120 DEG C, reaction carries out oxygenation pretreatment reaction in 4 hours；
(4) product that obtains in step (3) speed with 5 DEG C/min in psychrolusia is cooled down, with the speed of 4000r/min
Rate is centrifugal draws black liquor, adds 1g tripolycyanamide heated and stirred, freeze-day with constant temperature 12h in an oven, removes whole moisture, consolidate
Body mixture；
(5) transfer to, in corundum boat, transfer to afterwards in tube furnace by the solid mixture in step (4), with the speed that heats up
Rate is to keep after 2 DEG C/min rises to 400 DEG C within one hour, carrying out carbonization, is that 5 DEG C/min rises to 800 DEG C with heating rate the most again
Rear holding activates for one hour, and carbonization and activation use nitrogen to protect, and airflow rate is 800mL/min；
(6) reaction is cooled to room temperature after terminating, and the black powder distilled water of generation and ethanol alternately wash each 3 times, then
Removing whole moisture in 80 DEG C of freeze-day with constant temperature 12h, obtain the porous carbon materials in black, specific surface area has reached 1357m2/
g。
The SEM of porous carbon materials prepared by the present embodiment schemes as it is shown in figure 1, it can be seen that prepared by the present embodiment
Porous carbon materials there is loose structure and bigger specific surface area；
The graph of pore diameter distribution of porous carbon materials prepared by the present embodiment is as in figure 2 it is shown, it can be seen that the present embodiment
The aperture of the porous carbon materials of preparation is for being distributed as 0.5～3nm, and distribution is little.
Embodiment 8:
It is the ratio of 80:10:10 in mass ratio by made for embodiment 7 porous carbon materials and super P white carbon black, politef
Example mixes, and adds the even cream of ethanol furnishing, uses nickel foam to do collector, is coated in nickel foam, vacuum 0.1Pa at 50 DEG C
It is dried overnight, obtains carbon electrode.
Using the KOH of 6mol/L as electrolyte, assemble simulation ultracapacitor cell and be circulated volt-ampere and constant current charge and discharge
Electrical testing.
Test shows, after porous carbon materials prepared by the present embodiment makes super capacitor, under three electrode tests, than electricity
Hold and reached 296F/g.
Embodiment 9:
(1) first being dried by Caulis et Folium Oryzae and grind afterwards, then cross the steel sieve of 40 mesh, the Caulis et Folium Oryzae powder obtained is dried at 105 DEG C
12 hours；
(2) using KOH solution that mass concentration is 5% as the alkali liquor of Caulis et Folium Oryzae pretreatment, the rice straw powder that step (1) is obtained
End weighs the KOH solution of 10g with 100mL and mixes；
(3), after being stirred by the mixture in step (2), teflon-lined stainless steel cauldron is transferred to
In, at 120 DEG C, reaction carries out oxygenation pretreatment reaction in 5 hours；
(4) product that obtains in step (3) speed with 5 DEG C/min in psychrolusia is cooled down, with the speed of 4000r/min
Rate is centrifugal draws black liquor, adds 2g tripolycyanamide heated and stirred, freeze-day with constant temperature 12h in an oven, removes whole moisture, consolidate
Body mixture；
(5) transfer to, in corundum boat, transfer to afterwards in tube furnace by the solid mixture in step (4), use and heat up
Speed is to keep after 2 DEG C/min rises to 400 DEG C within one hour, carrying out carbonization, then is after 5 DEG C/min rises to 800 DEG C with heating rate
Keeping activating for one hour, carbonization and activation use nitrogen to protect, and airflow rate is 800mL/min；
(6) reaction is cooled to room temperature after terminating, and the black powder distilled water of generation and ethanol alternately wash each 3 times, then
Removing whole moisture in 80 DEG C of freeze-day with constant temperature 12h, obtain the porous carbon materials in black, specific surface area has reached 1357m2/
g。
The SEM of porous carbon materials prepared by the present embodiment schemes as it is shown on figure 3, it can be seen that prepared by the present embodiment
Porous carbon materials there is loose structure and bigger specific surface area；
The graph of pore diameter distribution of porous carbon materials prepared by the present embodiment as shown in Figure 4, it can be seen that the present embodiment
The aperture of the porous carbon materials of preparation is for being distributed as 0.5～3nm, and distribution is little.
Embodiment 10:
By made for embodiment 9 porous carbon materials and acetylene black, Kynoar, ratio for 80:10:10 in mass ratio is entered
Row mixing, adds the even cream of ethanol furnishing, uses nickel foam to do collector, is coated in nickel foam, and at 50 DEG C, vacuum 0.1Pa is dried
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assemble simulation ultracapacitor cell and be circulated volt-ampere and constant current charge and discharge
Electrical testing.
The cyclic voltammetry curve of carbon electrode prepared by the present embodiment and constant current charge-discharge curve are distinguished the most as shown in Figure 5 and Figure 6,
It can be seen that the carbon electrode that the present embodiment provides has good chemical property.
Test shows, after porous carbon materials prepared by the present embodiment makes super capacitor, under three electrode tests, than electricity
Hold and reached 337F/g.
Embodiment 11:
(1) first being dried by Caulis et Folium Oryzae and grind afterwards, then cross the steel sieve of 40 mesh, the Caulis et Folium Oryzae powder obtained is dried at 105 DEG C
12 hours；
(2) using KOH solution that mass concentration is 5% as the alkali liquor of Caulis et Folium Oryzae pretreatment, the rice straw powder that step (1) is obtained
End weighs the KOH solution of 10g with 100mL and mixes；
(3), after being stirred by the mixture in step (2), teflon-lined stainless steel cauldron is transferred to
In, at 120 DEG C, reaction carries out oxygenation pretreatment reaction in 6 hours；
(4) product that obtains in step (3) speed with 5 DEG C/min in psychrolusia is cooled down, with the speed of 4000r/min
Rate is centrifugal draws black liquor, adds 4g tripolycyanamide heated and stirred, freeze-day with constant temperature 12h in an oven, removes whole moisture, consolidate
Body mixture；
(5) transfer to, in corundum boat, transfer to afterwards in tube furnace by the solid mixture in step (4), use and heat up
Speed is to keep after 2 DEG C/min rises to 400 DEG C within one hour, carrying out carbonization, then is after 5 DEG C/min rises to 800 DEG C with heating rate
Keeping activating for one hour, carbonization and activation use argon to protect, and airflow rate is 800mL/min；
(6) reaction is cooled to room temperature after terminating, and the black powder distilled water of generation and ethanol alternately wash each 3 times, then
Removing whole moisture in 80 DEG C of freeze-day with constant temperature 12h, obtain the porous carbon materials in black, specific surface area has reached 1357m2/
g。
The SEM of porous carbon materials prepared by the present embodiment schemes as it is shown in fig. 7, it can be seen that prepared by the present embodiment
Porous carbon materials there is loose structure and bigger specific surface area；
The graph of pore diameter distribution of porous carbon materials prepared by the present embodiment as shown in Figure 8, it can be seen that the present embodiment
The aperture of the porous carbon materials of preparation is for being distributed as 0.5～3nm, and distribution is little.
Embodiment 12:
By made for embodiment 11 porous carbon materials and acetylene black, politef, ratio for 80:10:10 in mass ratio is entered
Row mixing, adds the even cream of ethanol furnishing, uses nickel foam to do collector, is coated in nickel foam, and at 50 DEG C, vacuum 0.1Pa is dried
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assemble simulation ultracapacitor cell and be circulated volt-ampere and constant current charge and discharge
Electrical testing.
Test shows, after porous carbon materials prepared by the present embodiment makes super capacitor, under three electrode tests, than electricity
Hold and reached 232F/g.
As can be seen from the above embodiments, porous carbon materials prepared by the preparation method that the present invention provides has high-ratio surface
Long-pending, the carbon electrode of preparation has good chemical property when super capacitor.
The above is only the preferred embodiment of the present invention, and the present invention not makees any pro forma restriction.Should
Point out, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to if making
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a preparation method for porous carbon materials, comprises the following steps:
(1) black liquid being carried out pretreatment, obtain solid mixture, described black liquid is containing of alkali paper-making generation
The waste liquid of KOH；
(2) solid mixture that described step (1) obtains is carried out carbonization, obtain material with carbon element；
(3) material with carbon element that described step (2) obtains is activated, obtain porous carbon materials.
Preparation method the most according to claim 1, it is characterised in that described in step (1), black liquid is before pretreatment
Mix with tripolycyanamide, obtain mixed solution.
Preparation method the most according to claim 2, it is characterised in that the quality of described tripolycyanamide is black liquid quality
0.5～2%.
Preparation method the most according to claim 1, it is characterised in that in described step (2), carbonization is in inert gas shielding
Under carry out.
5. according to the preparation method described in claim 1 or 4, it is characterised in that the temperature of described carbonization is 350～450 DEG C, carbon
The time changed is 0.5～1.5h.
Preparation method the most according to claim 1, it is characterised in that in described step (3), activation is in inert gas shielding
Under carry out.
7., according to the preparation method described in claim 1 or 6, it is characterised in that the temperature of described activation is 600～900 DEG C, live
The time changed is 0.5～1.5h.
8. the porous carbon materials that prepared by preparation method described in claim 1～7 any one, the specific surface of described porous carbon materials
Amass is 1500～3000m2/g。
Porous carbon materials the most according to claim 8, it is characterised in that the aperture of described porous carbon materials be 0.5～
3nm。
10. the application in ultracapacitor of the porous carbon materials described in claim 8 or 9.
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