CN106608627A - Mangnolia petal biological carbon of loose and porous structure and preparation method thereof - Google Patents
Mangnolia petal biological carbon of loose and porous structure and preparation method thereof Download PDFInfo
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- CN106608627A CN106608627A CN201610486348.5A CN201610486348A CN106608627A CN 106608627 A CN106608627 A CN 106608627A CN 201610486348 A CN201610486348 A CN 201610486348A CN 106608627 A CN106608627 A CN 106608627A
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- petal
- magnolia denudata
- loose
- porous structure
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000007772 electrode material Substances 0.000 claims abstract description 19
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 240000005819 Magnolia denudata Species 0.000 claims description 96
- 235000016094 Magnolia denudata Nutrition 0.000 claims description 96
- 238000001035 drying Methods 0.000 claims description 26
- 230000004913 activation Effects 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 18
- 239000000571 coke Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 238000005255 carburizing Methods 0.000 claims description 11
- 229910052756 noble gas Inorganic materials 0.000 claims description 10
- 150000002835 noble gases Chemical class 0.000 claims description 10
- 239000003082 abrasive agent Substances 0.000 claims description 8
- 239000003990 capacitor Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 240000002514 Cymbidium ensifolium Species 0.000 claims description 6
- 239000012620 biological material Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010348 incorporation Methods 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 241000628997 Flos Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- YLRXAIKMLINXQY-ZDUSSCGKSA-O (S)-magnoflorine Chemical compound C1=C(OC)C(O)=C2C3=C(O)C(OC)=CC=C3C[C@@H]3[N+](C)(C)CCC1=C23 YLRXAIKMLINXQY-ZDUSSCGKSA-O 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- KYEAXNAYHSCLMT-CVVGWEDFSA-N Magnoflorine Natural products C[C@H]1OC=C2[C@@H]3[C@@H]1CN4CCc5c([nH]c6ccccc56)[C@@H]4[C@@H]3OC2=O KYEAXNAYHSCLMT-CVVGWEDFSA-N 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000341 volatile oil Substances 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
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a mangnolia petal biological carbon of a loose and porous structure. The mangnolia petal biological carbon is a porous carbon material prepared in a way that mangnolia petal is taken as raw materials and is processed with a two-step method of high-temperature carbonization-activation. Firstly, dried mangnolia petals are carbonized at a proper temperature, then, KOH is taken as activating agent, and nitrogen is taken as protective gas to carry out high-temperature carbonization so as to obtain the mangnolia petal porous carbon. The carbon material prepared with the method has the advantages of large specific surface area, abundant raw materials and simple technology. When the carbon material is used as the electrode material of a supercapacitor, the carbon material has excellent capacitance performance and good cycling stability. The potential of the mangnolia petal in an energy field is highlighted, and the utilization value of the carbon material is expanded.
Description
Technical field
The invention belongs to plant resourcesizationes are using field and the preparation field of biomass carbon, it is more particularly to a kind of for super
Loose and porous structure Magnolia denudata petal biological carbon of capacitor electrode material and preparation method thereof.
Background technology
To reduce the consumption of Fossil fuel, alleviate energy crisis close at hand, prepared using pure-natural biological material
Porous carbon materials have broad prospects.The low raw-material cost of biomass porous carbon, abundance, and can effectively alleviate agriculture
The burden that industry by-product and offal treatment are caused, reclaims its value, turns waste into wealth, comply fully with environmentally friendly chemistry and
The requirement of Green Chemistry.Biological carbon preparation process has the advantages that rate of heat addition height, heating process are controllable, obtains loose structure carbon
Material have morphology controllable and can scale the characteristics of.
Magnolia denudata, also known as Flos micheliae Albae, Yutang spring, Flos Magnoliae, Flos micheliae Albae etc., it is Magnoliaceae magnolia.Original North America
The southeast, now cultivates in a large number as ornamental plant in China various places.It is mainly used in garden, park, avenue afforestation.Its leaf and petal
In containing various chemical compositions such as volatile oil, magnoflorine, with good medical value.At present, Magnolia denudata petal resource is ground
Study carefully and develop still at an early stage, therefore, research prepares Magnolia denudata petal biological carbon material tool and is of great significance.
The biological specific surface area of material with carbon element, the size in aperture and pore-size distribution still await changing obtained in prior art
Enter and the specific capacitance of unit mass is still low, cyclical stability is poor.That is, combination property is still not ideal enough.
At present, not yet find that Magnolia denudata petal prepares the relevant report of biomass carbon both at home and abroad.
The content of the invention
It is an object of the invention to provide a kind of loose and porous structure Magnolia denudata petal biological carbon and preparation method thereof.
According to the first embodiment of the present invention, there is provided a kind of loose and porous structure Magnolia denudata petal biological carbon, it is logical
Cross prepared by a kind of preparation method for comprising the following steps：
(1) raw material prepares：By Magnolia denudata petal cleaning, drying, crush, obtain dry Magnolia denudata petal raw material；
(2) it is carbonized：Dried Magnolia denudata petal raw material is taken, in being placed in carbide furnace (such as high temperature process furnances), in indifferent gas
Body is (such as N2) protection under be warming up to carburizing temperature (such as 500-800 DEG C, preferred 550-720 DEG C, more preferably 600-700 DEG C) and enter
Row carbonization (such as 1-5h, preferred 1.5-3h), obtains Magnolia denudata petal coke；
(3) activate：The Magnolia denudata petal coke of 1 weight portion is taken, with 1-6 weight portions, preferred 2-5 weight portions, more preferably 2-4 weights
The KOH mixing of amount part (such as 3 weight portions) (preferably mixes, incorporation time 30-60min, preferred 40- with KOH solid abrasives
50min).In being placed in carbide furnace (such as high temperature process furnances), in noble gases (such as N2) protection under be warming up to activation temperature (example
Such as 600-900 DEG C, preferred 620-850 DEG C, more preferably 700-800 DEG C) activated (such as 1-5h, preferred 1.5-3h), activate
The diluted mineral acid (such as 0.1～2.0M, preferably 0.5～1.0M) of material afterwards washs to neutrality or washs to acidity and wash with water
Wash to neutrality, finally by product drying to constant weight, that is, obtain required multiporous biological material with carbon element, i.e. loose and porous structure is beautiful
Cymbidium ensifolium (L.) Sw. lobe biological carbon.
Preferably, in step 1) in crushing, be crushed to 50 to 120 mesh, preferred 60-100 mesh, more preferably 70 to
90 mesh.
It is preferred that, gained loose and porous structure Magnolia denudata petal biological carbon has 1800m2g-1To 3200m2g-1, preferred 2050m2g-1To 3080m2g-1, more preferably 2320m2g-1To 2900m2g-1BET specific surface area；And/or
It is preferred that, loose and porous structure Magnolia denudata petal biological carbon has 1-7nm, preferred 1.2-6nm, more preferably 1.3-4nm, more
It is preferred that the average pore size of 1.4-3nm, more preferably 1.5-2nm, more preferably 1.6-1.97nm, such as 1.95nm.
It is preferred that, when loose and porous structure Magnolia denudata petal biological carbon is used as the electrode material of capacitor, in 0.5A g-1Electricity
Under current density, specific capacitance is higher than higher than 370F g-1, such as 374F g-1To 440F g-1, more preferably 385-435F g-1, it is more excellent
Select 400F g-1To 420F g-1。
According to the second embodiment of the present invention, there is provided a kind of preparation side of loose and porous structure Magnolia denudata petal biological carbon
Method provides a kind of method for preparing above-mentioned loose and porous structure Magnolia denudata petal biological carbon, and the method is comprised the following steps：
(1) raw material prepares：By Magnolia denudata petal cleaning, drying, crush, obtain dry Magnolia denudata petal raw material；
(2) it is carbonized：Dry Magnolia denudata petal raw material is taken, in being placed in carbide furnace (such as high temperature process furnances), in noble gases
(such as N2) protection under be warming up to carburizing temperature (such as 500-800 DEG C, preferred 550-720 DEG C, more preferably 600-700 DEG C) and carry out
Carbonization (such as 1-5h, preferred 1.5-3h), obtains Magnolia denudata petal coke；
(3) activate：The Magnolia denudata petal coke of 1 weight portion is taken, with 1-6 weight portions, preferred 2-5 weight portions, more preferably 2.5-4
The KOH mixing of weight portion (such as 3 weight portions) (preferably mixes, incorporation time 30-60min, preferred 40- with KOH solid abrasives
50min).In being placed in carbide furnace (such as high temperature process furnances), in noble gases (such as N2) protection under be warming up to activation temperature (example
Such as 600-900 DEG C, preferred 620-850 DEG C, more preferably 700-800 DEG C) activated (such as 1-5h, preferred 1.5-3h), activate
The diluted mineral acid (such as 0.1～2.0M, preferably 0.5～1.0M) of material afterwards washs to neutrality or washs to acidity and wash with water
Wash to neutrality, finally by product drying to constant weight, that is, obtain required multiporous biological material with carbon element, i.e. loose and porous structure is beautiful
Cymbidium ensifolium (L.) Sw. lobe biological carbon.
Preferably, in step 1) in crushing, be crushed to 50 to 120 mesh, preferred 60-100 mesh, more preferably 70 to
90 mesh.
It is preferred that, gained loose and porous structure Magnolia denudata petal biological carbon has 1800m2g-1To 3200m2g-1, preferred 2050m2g-1To 3080m2g-1, more preferably 2320m2g-1To 2900m2g-1BET specific surface area；And/or
It is preferred that, loose and porous structure Magnolia denudata petal biological carbon has 1-7nm, preferred 1.2-6nm, more preferably 1.3-4nm, more
It is preferred that the average pore size of 1.4-3nm, more preferably 1.5-2nm, more preferably 1.6-1.97nm.
It is preferred that, when loose and porous structure Magnolia denudata petal biological carbon is used as the electrode material of capacitor, in 0.5A g-1Electricity
Under current density, specific capacitance is higher than 370F g-1, such as 374F g-1To 440F g-1, more preferably 385-435F g-1, more preferably
400F g-1To 420F g-1。
In this application, in step (3), diluted mineral acid is dilute hydrochloric acid, dilute nitric acid, dilute sulphuric acid or dilute phosphoric acid
One kind, preferably dilute hydrochloric acid.For example its concentration be 0.1～2.0M, more preferably preferably 0.3～1.5M, 0.5～1.0M, more
It is preferred that 0.7～0.9M.
According to the third embodiment the present invention, there is provided loose and porous structure Magnolia denudata petal biological carbon or by said method
Purposes of the prepared loose and porous structure Magnolia denudata petal biological carbon as electrode material for super capacitor.
In an example of the application, biological carbon as electrode during electrode material for super capacitor manufacture method such as
Under：
Above-mentioned made biological carbon is adopted for active substance, conductive carbon black is conductive agent, ptfe emulsion (PTFE,
It is 60wt%) binding agent, and with nickel foam as collector.These three materials press 80:10:10 ratio is scattered in ethanol, is stirred
Ultrasound is mixed so that mix homogeneously, proceeds to mortar grinder, treats that ethanol evaporates into muddy, it is uniformly applied to foam nickel sheet.Thus
Made electrode keeps 5min compactings after being slightly dried with 10MPa pressure, places into that to be dried 12h in 130 DEG C of baking ovens standby.Material with carbon element
The load capacity of active substance is respectively in 4mg cm-2Left and right.
In an example of the application, obtained porous carbon materials BET specific surface area is up to 2928m2g-1, average pore size
For 2.07nm, during the electrode material as ultracapacitor, in 0.5A g-1Electric current density under, specific capacitance is up to 405F g-1。
For example, a kind of preparation method of loose and porous structure Magnolia denudata petal biological carbon of the invention is as follows：
(1) raw material prepares：Magnolia denudata petal clear water is washed away into debris, is crushed with pulverizer after drying, obtain dry jade
Cymbidium ensifolium (L.) Sw. lobe raw material；
(2) it is carbonized：Dried Magnolia denudata petal raw material is taken, in being placed in high temperature process furnances, in N2Protection under be warming up to one
Fixed carburizing temperature is carbonized, and obtains Magnolia denudata petal coke；
(3) activate：The Magnolia denudata petal coke of 1 weight portion is taken, is mixed with a certain amount of KOH solid abrasives.It is equal by mixing
Sample is placed in high temperature process furnances, in N2Protection under be warming up to certain activation temperature and activated, the material after activation is used
Dilute hydrochloric acid washs to neutrality or washs to acidity and be washed with water to neutrality, finally by product drying to constant weight, that is, needed for obtaining
The multiporous biological material with carbon element wanted, i.e. loose and porous structure Magnolia denudata petal biological carbon.
It is preferred that, in the step (1), Magnolia denudata petal is crushed to 80 mesh.
It is preferred that, in the step (2), heating rate is：4～5 DEG C/min；Carburizing temperature is：600～700 DEG C, preferably
650℃；Temperature retention time is 2h；
It is preferred that, in the step (3), add KOH solids weight be 2-4 weight portions, preferably 3 weight portions；During grinding
Between be：40-50min；Heating rate is：4～5 DEG C/min；Activation temperature is：700～800 DEG C, preferably 750 DEG C；Temperature retention time
For 2h；During cleaning, diluted mineral acid is dilute hydrochloric acid, and concentration is 0.5～1M.
In the present invention, loose and porous structure Magnolia denudata petal biological carbon is obtained using carbonization-KOH activation two-step methods, and is adopted
The Magnolia denudata petal biological carbon obtained with other activation methods is compared with optimum specific surface area, optimal pore-size distribution and optimal
Specific capacitance value.If using High Temperature High Pressure activation method, less, pore-size distribution is uneven for the Magnolia denudata petal carbon ratio surface area for obtaining
Even, specific capacitance is not high；If using boric acid either phosphoric acid or other acid (such as H2SO4Or HCl) activation, the Magnolia denudata Desr. for obtaining
Lobe biological carbon specific surface area very little, pore-size distribution is narrow, and specific capacitance is very low.The lifting of porous performance and capacitive property to material does not have
It is meaningful.
The present invention obtains following beneficial effect
1st, Magnolia denudata petal raw material is cheap, and carbonisation is simple to operation, and temperature-controllable, can be adapted to the life of amplification scale
Produce, bring considerable economic benefit.
2nd, the biological carbon specific surface area obtained by the present invention is big, even aperture distribution, and used as electrode material, specific capacitance is high,
Good cycling stability.
3rd, the step of present invention is using first carbonization reactivation, it is not necessary to carry out Alkaline pretreatment, and measured using KOH it is less, more
Environmental protection and energy saving, while the loose and porous structure Magnolia denudata petal biological carbon excellent performance for obtaining.
Description of the drawings
Fig. 1 is the pore size distribution curve of the biological carbon of example 2
Fig. 2 is the cyclic voltammetry figure of the biological carbon of example 2
Fig. 3 is the constant current charge-discharge test figure of the biological carbon of example 2
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be that following instance is served only for
The present invention is further described, it is impossible to is interpreted as limiting the scope of the invention, and person skilled in art can basis
Foregoing invention content makes some nonessential modifications and adaptations to the present invention.
The structural characterization of biological carbon passes through N in following instance2Absorption (Micromeritics TriStar II 3020) is surveyed
Examination.Specific surface area adopts adsorption isotherm according to Brunauer-Emmett-Teller (BET) Theoretical Calculation, pore-size distribution (PSD)
The absorption of line is simultaneously calculated using Barrett-Joyner-Halenda (BJH) model.
Raw material, reagent and instrument used in embodiment：
Magnolia denudata petal：Pluck in the campus of xiangtan, hunan province.
KOH：Aladdin chemical reagents corporation, AR.
HCl：Tianjin Fu Yu Fine Chemical Co., Ltd, AR.
Politef：Aladdin chemical reagents corporation, 60wt%.
N2：Zhong Tai Hongyuans, Hunan gas company limited.
Dehydrated alcohol：Tianjin great Mao chemical reagent factories, AR.
Nickel foam：Changsha Liyuan New Material Co., Ltd..
Pulverizer：Beijing Ge Ruideman experimental instruments and equipment limiteds, HM100.
Specific surface area and Porosimetry：Micromeritics companies of the U.S., Tristar II 3020.
Electrochemical workstation：Shanghai Chen Hua Instrument Ltd., CHI760D.
Biological carbon is as follows as the manufacture method of electrode during electrode material for super capacitor in following instance：
Above-mentioned made biological carbon is adopted for active substance, conductive carbon black is conductive agent, ptfe emulsion (PTFE,
It is 60wt%) binding agent, and with nickel foam as collector.These three materials press 80:10:10 ratio is scattered in ethanol, is stirred
Ultrasound is mixed so that mix homogeneously, proceeds to mortar grinder, treats that ethanol evaporates into muddy, it is uniformly applied to foam nickel sheet.Thus
Made electrode keeps 5min compactings after being slightly dried with 10MPa pressure, places into that to be dried 12h in 130 DEG C of baking ovens standby.Material with carbon element
The load capacity of active substance is respectively in 4mg cm-2Left and right.
To carry out electrochemical test method as the electrode material of ultracapacitor as follows for biological carbon in following instance：
Unipolar capacitive property is tested using CHI760D electrochemical workstation three-electrode systems, wherein to electrode
For platinum electrode, Hg/HgO is reference electrode, and 6M KOH solutions are electrolyte.This example mainly using cyclic voltammetry (CV),
The method such as constant current charge-discharge (GC) and electrochemical impedance spectroscopy (EIS) carries out electrochemical property test.The circulation of single electrode
Volt-ampere test voltage range set is -1～0V.The electric current density of charge-discharge test is arranged on 0.5～20A g-1, and voltage range
For -1～0V.Cycle charge discharge electrical testing is carried out by two electrode systems, and electric current density is set to 1A g-1, wherein to electrode and ginseng
It is same electrode than electrode, operating voltage range is set as 0～1V.
The specific capacitance of material with carbon element is calculated by the electric discharge of constant current charge-discharge according to below equation：
Cg=I/ (mdV/dt)
Wherein I is constant current, and m is the quality of active substance, and dV/dt is according to the discharge curve for removing voltage drop part
Slope obtained by calculating.
Example 1
Magnolia denudata petal clear water is washed away into debris, pulverizer is crushed to 80 mesh after drying.10g Magnolia denudata petal powder is taken, is put
In high temperature process furnances, in N2Protection under press 5 DEG C of min-1To 650 DEG C, constant temperature carbonization 2h takes out carbon to ramp under room temperature
Compound, obtains non-activated Magnolia denudata petal coke 2.8g.Magnolia denudata petal coke is mixed with 8.4g KOH solid abrasives.Will mixing
Equal sample is placed in high temperature process furnances, in noble gases (such as N2) protection under be warming up to 700 DEG C and activated, soak time
3h, takes out the material after activation and is washed till neutrality with the HCl of 1.0M, finally by product drying to constant weight, obtains 0.66g loose many
Pore structure Magnolia denudata petal biological carbon.BET specific surface area is up to 2396m2g-1, average pore size is 1.97nm, and with preferable hole
Footpath is distributed.During the electrode material as ultracapacitor, in 0.5A g-1Electric current density under, specific capacitance be 374F g-1。
Example 2
Magnolia denudata petal clear water is washed away into debris, pulverizer is crushed to 80 mesh.10g Magnolia denudata petal powder is taken, high temperature is placed in
In tube furnace, in N2Protection under press 5 DEG C of min-1To 650 DEG C, constant temperature carbonization 2h takes out carbide to ramp under room temperature, obtains
To non-activated Magnolia denudata petal coke 2.8g.Magnolia denudata petal coke is mixed with 8.4g KOH solid abrasives.Equal sample will be mixed
Product are placed in high temperature process furnances, in noble gases (such as N2) protection under be warming up to 750 DEG C and activated, soak time 3h takes
The material gone out after activation is washed till neutrality with the HCl of 1.0M, finally by product drying to constant weight, obtains 0.58g loose and porous structures
Magnolia denudata petal biological carbon.
The biological carbon BET specific surface area for preparing as shown in Figure 1 is up to 2928m2g-1, average pore size is 1.83nm, and is had
Preferably the size or size in pore-size distribution footpath is than more uniform.As shown in Figure 2, CV curves are close to the rectangle of rule, show electrode
Material has preferable capacitive property, can be rapidly performed by the absorption of ion and exchange.From the figure 3, it may be seen that GC curves are presented symmetrical
Triangle, when showing that biological carbon is used as the electrode material of ultracapacitor, in 0.5A g-1Electric current density under, specific capacitance is high
Up to 405F g-1。
Example 3
Magnolia denudata petal clear water is washed away into debris, pulverizer is crushed to 80 mesh.10g Magnolia denudata petal powder is taken, high temperature is placed in
In tube furnace, in N2Protection under press 5 DEG C of min-1To 650 DEG C, constant temperature carbonization 2h takes out carbide to ramp under room temperature, obtains
To non-activated Magnolia denudata petal coke 2.8g.Magnolia denudata petal coke is mixed with 8.4g KOH solid abrasives.Equal sample will be mixed
Product are placed in high temperature process furnances, in noble gases (such as N2) protection under be warming up to 800 DEG C and activated, soak time 3h takes
The material gone out after activation is washed till neutrality with the HCl of 1.0M, finally by product drying to constant weight, obtains 0.52g loose and porous structures
Magnolia denudata petal biological carbon.BET specific surface area is up to 2630m2g-1, average pore size is 1.93nm, and with preferable pore-size distribution.
During the electrode material as ultracapacitor, in 0.5A g-1Electric current density under, specific capacitance be 385F g-1。
Embodiment 4
Repeat embodiment 1, simply Magnolia denudata petal is crushed to 70 mesh, 600 DEG C of carburizing temperature, carbonization time 3h.KOH solids
Quality is identical with activation temperature.Obtain Magnolia denudata petal porous carbon.BET specific surface area is up to 2482m2g-1, average pore size is
1.96nm。
Embodiment 5
Repeat embodiment 1, simply 700 DEG C of carburizing temperature, soak time 1.5h, are washed after activation with the dust technology of 2.0M.
The quality of KOH solids is identical with activation temperature.Obtain Magnolia denudata petal porous carbon.BET specific surface area is up to 2531m2g-1, average hole
Footpath is 1.94nm.
Embodiment 6
Repeat embodiment 1, simply the quality of KOH solids is 5.6g, carburizing temperature is identical with activation temperature, obtains Magnolia denudata Desr.
Lobe porous carbon.BET specific surface area is up to 2331m2g-1, average pore size is 1.97nm.
Embodiment 7
Repeat embodiment 1, simply the quality of KOH solids is 11.2g, carburizing temperature is identical with activation temperature, obtains Magnolia denudata
Petal porous carbon.BET specific surface area is up to 2631m2g-1, average pore size is 1.93nm.
Comparative example 1
Magnolia denudata petal clear water is washed away into debris, pulverizer is crushed to 80 mesh after drying.10g Magnolia denudata Desr. powder is taken, is put into
In the KOH solution of 200mL 1M, in high pressure rustless steel kettle, 120 DEG C of pyroreactions 2h, subsequent directly filtration drying.Will activation
Dried sample is placed in high temperature process furnances, in N2Protection under press 5 DEG C of min-1To 700 DEG C, constant temperature is carbonized ramp
Carbide is taken out under 2h, room temperature, with ultrapure neutrality is washed to.Finally by product drying to constant weight, high pressure hydro-thermal Magnolia denudata Desr. is obtained
Lobe biological carbon 0.23g.BET specific surface area is 1331m2g-1, average pore size is 5.81nm.Capacitance is 252F g-1。
Comparative example 2
Magnolia denudata petal clear water is washed away into debris, pulverizer is crushed to 80 mesh after drying.10g Magnolia denudata petal powder is taken, is put
In entering the boric acid solution of 200mL 1.5M, in high pressure rustless steel kettle, 120 DEG C of pyroreactions 2h, subsequent directly filtration drying.Will
Activate dried sample to be placed in high temperature process furnances, in N2Protection under press 5 DEG C of min-1Ramp to 700 DEG C, constant temperature carbon
Change 2h, under room temperature carbide is taken out, with ultrapure neutrality is washed to.Finally by product drying to constant weight, the B doping biological carbons of preparation
BET specific surface area is 1010m2g-1, during the electrode material as ultracapacitor, in 0.5A g-1Electric current density under, specific capacitance
For 210F g-1
Comparative example 3
Magnolia denudata petal clear water is washed away into debris, pulverizer is crushed to 80 mesh after drying.10g Magnolia denudata petal powder is taken, is put
In entering the phosphoric acid solution of 200mL 1.5M, in high pressure rustless steel kettle, 120 DEG C of pyroreactions 2h, subsequent directly filtration drying.Will
Activate dried sample to be placed in high temperature process furnances, in N2Protection under press 5 DEG C of min-1Ramp to 700 DEG C, constant temperature carbon
Change 2h, under room temperature carbide is taken out, with ultrapure neutrality is washed to.Finally by product drying to constant weight, the P doping biological carbons of preparation
BET specific surface area is 1123m2g-1, during the electrode material as ultracapacitor, in 0.5A g-1Electric current density under, specific capacitance
For 221F g-1。
Comparative example 4
Magnolia denudata petal clear water is washed away into debris, pulverizer is crushed to 80 mesh after drying.10g Magnolia denudata petal powder is taken, is put
In entering the hydrochloric acid solution of 200mL 1.5M, in high pressure rustless steel kettle, 120 DEG C of pyroreactions 2h, subsequent directly filtration drying.Will
Activate dried sample to be placed in high temperature process furnances, in N2Protection under press 5 DEG C of min-1Ramp to 700 DEG C, constant temperature carbon
Change 2h, under room temperature carbide is taken out, with ultrapure neutrality is washed to.Finally by product drying to constant weight, it is impossible to obtain codope beautiful
Cymbidium ensifolium (L.) Sw. lobe porous carbon.N (wt%) content is 1.5%, and the biological carbon BET specific surface area for preparing as shown in Figure 1 is 1012m2g-1, use
When making the electrode material of ultracapacitor, in 0.5A g-1Electric current density under, specific capacitance be 211F g-1。
Claims (10)
1. a kind of loose and porous structure Magnolia denudata petal biological carbon, it is prepared by a kind of preparation method by comprising the following steps
's：
(1) raw material prepares：By Magnolia denudata petal cleaning, drying, crush, obtain dry Magnolia denudata petal raw material；
(2) it is carbonized：Dried Magnolia denudata petal raw material is taken, in being placed in carbide furnace (such as high temperature process furnances), in noble gases (such as
N2) protection under be warming up to carburizing temperature (such as 500-800 DEG C, preferred 550-720 DEG C, more preferably 600-700 DEG C) and carry out carbon
Change (such as 1-5h, preferred 1.5-3h), obtain Magnolia denudata petal coke；
(3) activate：The Magnolia denudata petal coke of 1 weight portion is taken, with 1-6 weight portions, preferred 1.5-5.5 weight portions, more preferably 2-5 weights
The KOH mixing of amount part (such as 3 or 4 weight portions) (preferably mixes, incorporation time 30-60min, preferred 40- with KOH solid abrasives
50min), in being placed in carbide furnace (such as high temperature process furnances), in noble gases (such as N2) protection under be warming up to activation temperature (example
Such as 600-900 DEG C, preferred 620-850 DEG C, more preferably 700-800 DEG C) activated (such as 1-5h, preferred 1.5-3h), activate
The diluted mineral acid (such as 0.1～2.0M, preferably 0.5～1.0M) of material afterwards washs to neutrality or washs to acidity and wash with water
Wash to neutrality, finally by product drying to constant weight, that is, obtain required multiporous biological material with carbon element, i.e. loose and porous structure is beautiful
Cymbidium ensifolium (L.) Sw. lobe biological carbon.
2. loose and porous structure Magnolia denudata petal biological carbon according to claim 1, wherein in step 1) in crushing, crush
To 50 to 120 mesh, more preferably preferred 60-100 mesh, 70 to 90 mesh.
3. according to the loose and porous structure Magnolia denudata petal biological carbon of claim 1 or 2, wherein loose and porous structure Magnolia denudata petal life
Thing carbon has 1800m2g-1To 3200m2g-1, preferred 2050m2g-1To 3080m2g-1, more preferably 2320m2g-1To 2900m2g-1's
BET specific surface area；And/or
Wherein loose and porous structure Magnolia denudata petal biological carbon has 1-7nm, preferred 1.2-6nm, more preferably 1.3-4nm, more preferably
The average pore size of 1.4-3nm, more preferably 1.5-2nm, more preferably 1.6-1.97nm.
4. according to the loose and porous structure Magnolia denudata petal biological carbon of claim 1 or 2 or 3, wherein, when loose and porous structure Magnolia denudata
When petal biological carbon is used as the electrode material of capacitor, in 0.5A g-1Electric current density under, specific capacitance is higher than 370F g-1,
Such as 374F g-1To 440F g-1, more preferably 385-435F g-1, more preferably 400F g-1To 420F g-1。
5. a kind of preparation method or one kind of loose and porous structure Magnolia denudata petal biological carbon prepares any one in claim 1-4
Loose and porous structure Magnolia denudata petal biological carbon method, the method comprises the following steps：
(1) raw material prepares：By Magnolia denudata petal cleaning, drying, crush, obtain dry Magnolia denudata petal raw material；
(2) it is carbonized：Dried Magnolia denudata petal raw material is taken, in being placed in carbide furnace (such as high temperature process furnances), in noble gases (such as
N2) protection under be warming up to carburizing temperature (such as 500-800 DEG C, preferred 550-720 DEG C, more preferably 600-700 DEG C) and carry out carbon
Change (such as 1-5h, preferred 1.5-3h), obtain Magnolia denudata petal coke；
(3) activate：The Magnolia denudata petal coke of 1 weight portion is taken, with 1-6 weight portions, more preferably preferred 2-5 weight portions, 2.5-4 weight
KOH mixing (preferably mixing with KOH solid abrasives, incorporation time 30-60min, preferred 40-50min) of part (such as 3 weight portions),
In being placed in carbide furnace (such as high temperature process furnances), in noble gases (such as N2) protection under be warming up to activation temperature (such as 600-
900 DEG C, preferred 620-850 DEG C, more preferably 700-800 DEG C) activated (such as 1-5h, preferred 1.5-3h), the material after activation
Material diluted mineral acid (such as 0.1～2.0M, preferably 0.5～1.0M) is washed to neutral or wash to acidity and be washed with water to
Property, finally by product drying to constant weight, that is, obtain required multiporous biological material with carbon element, i.e. loose and porous structure Magnolia denudata petal
Biological carbon.
6. method according to claim 5, wherein for the crushing in step (1), being crushed to 50 to 120 mesh, preferably
60-100 mesh, more preferably 70 to 90 mesh.
7. the method according to claim 5 or 6, wherein in the carbonization of the step (2), heating rate is 4～5 DEG C of min-1, carburizing temperature is 600～700 DEG C, and temperature retention time is 2-3h.
8. the method according to claim 5 or 6 or 7, wherein for grinding in step (3), milling time is 40-50min,
Heating rate is 4～5 DEG C of min-1, activation temperature is 700～800 DEG C, and temperature retention time is 2-3h；Concentration is 0.5 during cleaning
The dilute hydrochloric acid of～1.0M.
9. the loose and porous structure Magnolia denudata petal biological carbon for being prepared by the method according to claim 5 or 6 or 7 or 8, its
In：
Gained loose and porous structure Magnolia denudata petal biological carbon has 1800m2g-1To 3200m2g-1, preferred 2050m2g-1Extremely
3080m2g-1, more preferably 2320m2g-1To 2900m2g-1BET specific surface area；And/or
Wherein loose and porous structure Magnolia denudata petal biological carbon has 1-7nm, preferred 1.2-6nm, more preferably 1.3-4nm, more preferably
The average pore size of 1.4-3nm, more preferably 1.5-2nm, more preferably 1.6-1.97nm.
10. the loose and porous structure Magnolia denudata petal biological carbon of any one or by any in claim 5-9 in claim 1-4
The purposes of the loose and porous structure Magnolia denudata petal biological carbon prepared by the method for, it is characterised in that：Loose and porous structure is beautiful
Cymbidium ensifolium (L.) Sw. lobe biological carbon is used as the electrode material of capacitor or ultracapacitor.
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