CN108726517A - The method for improving rice husk base capacitance carbon volumetric capacitance - Google Patents
The method for improving rice husk base capacitance carbon volumetric capacitance Download PDFInfo
- Publication number
- CN108726517A CN108726517A CN201810807326.3A CN201810807326A CN108726517A CN 108726517 A CN108726517 A CN 108726517A CN 201810807326 A CN201810807326 A CN 201810807326A CN 108726517 A CN108726517 A CN 108726517A
- Authority
- CN
- China
- Prior art keywords
- carbon
- capacitance
- rice husk
- pitch
- warming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 235000007164 Oryza sativa Nutrition 0.000 title claims abstract description 84
- 235000009566 rice Nutrition 0.000 title claims abstract description 84
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- 239000010903 husk Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 34
- 240000007594 Oryza sativa Species 0.000 title 1
- 241000209094 Oryza Species 0.000 claims abstract description 83
- 239000002296 pyrolytic carbon Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 238000000197 pyrolysis Methods 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 34
- 238000010792 warming Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006555 catalytic reaction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000010426 asphalt Substances 0.000 claims description 10
- 239000003610 charcoal Substances 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 abstract description 7
- 238000006297 dehydration reaction Methods 0.000 abstract description 7
- 239000002028 Biomass Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 238000002309 gasification Methods 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000001994 activation Methods 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the methods for improving rice husk base capacitance carbon volumetric capacitance, belong to biomass energy chemical field, improve tap density using three kinds of methods, improve volumetric capacitance；It is specifically related to：(1) using the solid Pd/carbon catalyst impregnation of dehydration, temperature control pyrolysis increases fixed carbon content；(2) after the desiliconization of pyrolytic carbon hydro-thermal, template carbon is handled using impregnating pitch, fills the micropore of gasification zone, improves tap density；(3) electrode pitch modification capacitance carbon surface is used, electric conductivity and tap density are improved.Compared with prior art, the present invention prepares rice husk base capacitance carbon by different modification processing methods, improves tap density, volumetric capacitance, cyclical stability and the capacitance Carbon yield of capacitance carbon.
Description
Technical field
The invention belongs to biomass energy chemical fields, disclose a kind of side for improving rice husk base capacitance carbon volumetric capacitance
Method, and in particular to the solid Pd/carbon catalyst dipping rice husk of dehydration, impregnating pitch processing template charcoal, electrode pitch modification capacitance carbon carry
The method of high rice hull carbon volumetric capacitance.
Background technology
Biological material has the characteristics that derive from a wealth of sources, is environmental-friendly.In recent years, it is that raw material prepares capacitance using biomass
Charcoal has obtained extensive concern.Rice husk is a kind of cheap, huge renewable biomass resources of yield, using rice husk as raw material
The capacitance carbon of preparation has the structure of multistage pore canal and larger specific surface area, but rice husk base capacitance carbon is as super capacitor
The main problem of device electrode material is that rice husk fixation carbon content is low, and the volumetric capacitance as ultracapacitor is small, single in storage
The volume that bigger is needed when the capacitance of position quality, keeps its commerciality relatively low, is unfavorable for practical application.
In order to improve the volumetric capacitance of rice husk base capacitance carbon, the present invention uses heat after the solid Pd/carbon catalyst processing rice husk of dehydration
Solution, then desiliconization pyrolytic carbon is modified with impregnating pitch, after activation, then with electrode bitumen treatment.Pitch is a kind of fixed carbon content
The preferable material of higher and electric conductivity, using pitch to desiliconization pyrolytic carbon and the activated carbon modified vibration density that can improve material
Degree improves volumetric capacitance, the electric conductivity of material is also added, to promote chemical property, as notification number is
The Chinese patent literature of " CN107364863A " discloses the preparation method of modified rice husk matrix activated carbon, is effectively improved rice
Volumetric capacitance and cyclical stability of the based active carbon as electrode material.The solid Pd/carbon catalyst of dehydration is in pyrolytic process to rice husk
Catalytic dehydration, control temperature increases rice husk dewatering time in pyrolytic process, reduces the generation of gas phase and liquid phase, solid to increase
The content of phase, and then the yield of rice hull carbon is promoted, promote the volumetric capacitance of capacitance carbon.
At present rice husk base capacitance carbon there are the problem of：
1, for a large amount of carbon with gaseous state and liquid drain, fixed carbon content is few in pyrolytic process for rice husk；
2, the electric conductivity of rice husk capacitance carbon is poor so that electrolyte ion transport difficult；
3, tap density is low, influences volumetric capacitance.
Therefore a kind of new technical solution is needed to solve the problems, such as this in the prior art.
Invention content
During rice husk thermal decomposition, volatile matter effusion forms a large amount of micropores, the tap density of pyrolytic carbon is relatively low, through desiliconization
After activation, the tap density of capacitance carbon is lower, causes volumetric capacitance low, and the capacitor storage ability of same volume is small, this is
Rice hull carbon (or biomass carbon) is constrained in the application of energy-storage battery and ultracapacitor field, the object of the present invention is to provide carry
The method of high rice hull carbon volumetric capacitance, using rice husk as charcoal source, by catalyst treatment, charing, asphalt modification desiliconization pyrolytic carbon,
Asphalt modification capacitance carbon and etc. prepare modified rice husk base capacitance Carbon Materials.Prepared material is with electrochemical stability
Electrode material for super capacitor characteristic good, volumetric capacitance is high, and its is at low cost, pollution is small, environmental-friendly, it can be extensive
Production.
In order to achieve the above object, the present invention adopts the following technical scheme that：Improve rice husk base capacitance carbon volumetric capacitance
Method, which is characterized in that this method comprises the following steps：
It cleans Step 1: rice husk is sieved, crushes, obtain powdered rice hulls, powdered rice hulls are soaked after being mixed with catalyst solution
Stain processing, after impregnation, is down to room temperature and is filtered, filter cake is placed at 80 DEG C~100 DEG C and is dried, is pre-processed
Rice husk；
Step 2: the pretreatment rice husk prepared by step 1 is placed in tube furnace, 200 DEG C~300 DEG C are first warming up to, heat
0.5h is solved, then is warming up to 500 DEG C~600 DEG C and is pyrolyzed 1h under nitrogen protection, room temperature is down to, obtains pyrolytic carbon；
Step 3: pressing solid-to-liquid ratio 1Kg：The ratio of 10L is by the NaOH of the pyrolytic carbon obtained in step 2 and a concentration of 5wt%
Solution is added in reaction kettle, heating reflux reaction 2h, and cooling is separated by filtration, filter cake is washed till neutrality, dries, obtains desiliconization
Pyrolytic carbon；
Step 4: the desiliconization pyrolytic carbon that step 3 obtains is uniformly mixed with impregnating pitch, it is placed in reaction kettle, is warming up to
150 DEG C~250 DEG C, 2h~5h is impregnated under conditions of pressure is 0.1MPa~0.6MPa and obtains bituminizing forerunner after cooling
Body；
Step 5: the bituminizing presoma that step 4 obtains is transferred in tube furnace, it is warming up to 600 DEG C~1000 DEG C
1h~2h is carbonized, bituminizing pyrolytic carbon is prepared；
Step 6: the bituminizing pyrolytic carbon prepared by step 5 is handled to obtain powdered carbon, powdered carbon is with alkali according to charcoal
Alkali is than 1:(2.0~2.5) it is uniformly mixed, is placed in tube furnace, be first warming up to 450 DEG C with the heating rate of 5 DEG C/min, keep
0.5h is further continued for being warming up to 700 DEG C with the heating rate of 5 DEG C/min, keeps 1h, be cooled to room temperature taking-up, use hot deionized water
It is washed till neutrality, in 120 DEG C of drying, prepares catalysis rice husk/asphaltic base capacitance carbon.
The method for improving rice husk base capacitance carbon volumetric capacitance, using above-mentioned steps one to the method described in step 6,
It is characterized in that, further includes：
Step 7: the preparation of asphalt modification capacitance carbon：
(1) catalysis rice husk/asphaltic base capacitance carbon prepared by step 6 is added in pitch suspension, is dispersed with stirring
0.5h~2h, heating recovery solvent, solid are placed in drying box, 85 DEG C of dry 5h~12h, prepare pitch/capacitance carbon mixing
Powder；
(2) pitch/capacitance carbon mixed-powder prepared by step (1) is transferred in tube furnace, under nitrogen protection, heating
It is heat-treated 1h~2h to 150 DEG C~250 DEG C constant temperature, then is warming up to 600 DEG C~1000 DEG C constant temperature heat treatment 1h~2h, cooling is beaten
It dissipates, prepares asphalt modification capacitance carbon.
Impregnation process described in step 1 is as follows：Reaction kettle, sealing, profit is added in powdered rice hulls and catalyst solution
It is heated with steam, heating temperature is 120 DEG C~130 DEG C, impregnating by pressure 1h；Or the temperature of heating systems is 30 DEG C~50 DEG C, it is permanent
Temperature dipping is for 24 hours.
Catalyst in the step 1 is NH4Cl、NH4OH、HCl、H2SO4、H3PO4It is one such or two kinds or more
Mixture.
The mass concentration of the catalyst solution of the step 1 is 0%~20%.
The powdered rice hulls of the step 1 and the solid-to-liquid ratio of catalyst solution are 1Kg:(5~20) L.
The preparation method of pitch suspension in the step 7 is：Asphalt powder is added in solvent, is dispersed with stirring 0.5
~2h obtains pitch suspension.
The ratio of pitch and catalysis rice husk/asphaltic base capacitance carbon solid content is (10~30) in the step 7：100.
Solvent in the step 7 is a kind of in cyclohexanol, absolute ethyl alcohol, acetone, tetrahydrofuran, hexamethylene, n-hexane
Or two kinds of mixture.
The solid-to-liquid ratio of the pitch and solvent is (5Kg~15Kg):100L.
By above-mentioned design scheme, the present invention can bring following advantageous effect：
1, rice husk used is a kind of reproducible biomass resource, and the process of preparation is pollution-free and cheap；Pitch
Material source is extensive, low cost, environmental-friendly, can be mass-produced.
2, solid Pd/carbon catalyst handles rice husk, promotes dehydration, reduces the loss of rice husk gas phase and liquid phase in carbonization process, increases
It is fixed carbon content.
3, pitch can form flowable state when reaching softening point temperature, and the pitch of flowable state can be right in activation process
Modified pyrolytic carbon modification, to effectively improve the chemical property of material.
4, the fixation carbon content of pitch is higher, and the tap density of activated carbon can be improved with rice husk pyrolytic carbon co-activating, from
And improve the volumetric capacitance of material.
5, template carbon is handled using impregnating pitch, and thin powdered carbon is wrapped in particle surface and unifies grain size, and fills gasification zone
Tap density is improved in the micropore come.
Description of the drawings
Fig. 1 is the ratio electricity of the embodiment of the present invention 1 and embodiment 2 constant current charge-discharge 20000 times when current density is 1A/g
Hold and cycle number of turns schematic diagram.
Specific implementation mode
In order to clearly illustrate that the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.In order to avoid obscuring the essence of the present invention, well known method and process are not described in detail.
Embodiment 1
(1) raw rice husk is sieved and is cleaned, it is 10mm~20mm to be crushed to grain size, obtains powdered rice hulls, spare；
(2) powdered rice hulls that step (1) obtains are placed in tube furnace, under nitrogen protection, with the heating rate of 5 DEG C/min
200 DEG C, pyrolysis dehydration 0.5h are warming up to, then 500 DEG C are warming up to the heating rate of 5 DEG C/min, 1h is pyrolyzed, obtains pyrolytic carbon；
(3) NaOH solution of the pyrolytic carbon and a concentration of 5wt% that obtain step (2) is according to solid-to-liquid ratio 1Kg:10L is mixed,
It is heated to reflux 2h, is cooled to room temperature suction filtration, filter cake is washed to neutrality, and drying obtains desiliconization rice husk pyrolytic carbon；
(4) the desiliconization rice husk pyrolytic carbon for obtaining step (3) and sodium hydroxide are according to mass ratio 1:2.5 are added to high mixer
Middle mixing, is transferred in the tube furnace of nitrogen protection, is first warming up to 450 DEG C of holding 0.5h with the heating rate of 5 DEG C/min, then with
The heating rate of 5 DEG C/min is warming up to 700 DEG C, keeps 1h, is cooled to room temperature and is washed till neutrality, dried at 120 DEG C, obtain rice husk
Base capacitance carbon AC1.
Embodiment 2
(1) raw rice husk is sieved and is cleaned, it is 10mm~20mm, the NH with a concentration of 5wt% to be crushed to grain size4OH solution
According to solid-to-liquid ratio 1Kg：10L is added in reaction kettle, and heated sealed is cooled to room temperature suction filtration to 120 DEG C, impregnating by pressure 1h, filter
It is recycled after liquid adjustment concentration, filter cake is dried at 100 DEG C, obtains catalyst treatment rice husk, spare；
(2) the catalyst treatment rice husk that step (1) obtains is placed in tube furnace, under nitrogen protection, with 5 DEG C/min's
Heating rate is warming up to 200 DEG C, is pyrolyzed 0.5h, then be warming up to 500 DEG C with the heating rate of 5 DEG C/min, is pyrolyzed 1h, is pyrolyzed
Charcoal；
(3) pyrolytic carbon for obtaining step (2) is according to solid-to-liquid ratio 1Kg:10L is mixed with the NaOH solution of a concentration of 5wt%,
It is heated to reflux 2h, is cooled to room temperature suction filtration, filter cake is washed to neutrality, dries, obtains desiliconization pyrolytic carbon；
(4) according to charcoal alkali mass ratio 1:2.5, desiliconization pyrolytic carbon and sodium hydroxide addition that step (3) obtains are placed in nitrogen
In the tube furnace of gas shielded, 450 DEG C of holding 0.5h are first warming up to the heating rate of 5 DEG C/min, then with the heating speed of 5 DEG C/min
Rate is warming up to 700 DEG C, keeps 1h, is cooled to room temperature and is washed till neutrality, dried at 120 DEG C, obtains catalysis rice husk base capacitance carbon
AC2。
Embodiment 3
(1) raw rice husk is sieved and is cleaned, it is 10mm~20mm, the NH with a concentration of 5wt% to be crushed to grain size4OH solution
According to solid-to-liquid ratio 1Kg:10L is added in reaction kettle, and heated sealed is cooled to room temperature suction filtration to 120 DEG C, impregnating by pressure 1h, filter
It is recycled after liquid adjustment concentration, filter cake is dried at 100 DEG C, obtains catalyst treatment rice husk, spare；
(2) the catalyst treatment rice husk that step (1) obtains is placed in tube furnace, under nitrogen protection, first with 5 DEG C/min
Heating rate be warming up to 200 DEG C, be pyrolyzed 0.5h, then 500 DEG C are warming up to heating rate, be pyrolyzed 1h, obtain catalysis pyrolytic carbon；
(3) the catalysis pyrolytic carbon for obtaining step (2) is according to solid-to-liquid ratio 1Kg:The NaOH solution of 10L and a concentration of 5wt%
Mixing, is heated to reflux 2h, is cooled to room temperature suction filtration, filter cake is washed to neutrality, dries, obtains desiliconization pyrolytic carbon；
(4) it is 4 according to mass ratio:1, the desiliconization pyrolytic carbon that step (3) obtains is uniformly mixed with impregnating pitch, is placed in anti-
It answers in kettle, is warming up to 200 DEG C, 2h is impregnated under the conditions of pressure is 0.5MPa and obtains bituminizing pyrolytic carbon after cooling；
(5) according to charcoal alkali mass ratio 1:2.5, bituminizing pyrolytic carbon and sodium hydroxide addition that step (4) obtains are set
In the tube furnace of nitrogen protection, 450 DEG C of holding 0.5h are first warming up to the heating rate of 5 DEG C/min, then with the liter of 5 DEG C/min
Warm rate is warming up to 700 DEG C, keeps 1h, is cooled to room temperature and is washed till neutrality, dried at 120 DEG C, obtains catalysis rice husk/asphaltic base
Capacitance carbon AC3.
Embodiment 4
It is 6 according to mass ratio:1, the desiliconization pyrolytic carbon that step (3) obtains is uniformly mixed with impregnating pitch, is placed in reaction
In kettle, other conditions are consistent with embodiment 3, obtain catalysis rice husk/asphaltic base capacitance carbon AC4.
Embodiment 5
It is 8 according to mass ratio:1, the desiliconization pyrolytic carbon that step (3) obtains is uniformly mixed with impregnating pitch, is placed in reaction
In kettle, other conditions are consistent with embodiment 3, obtain catalysis rice husk/asphaltic base capacitance carbon AC5.
Embodiment 6
It is 10 according to mass ratio:1, the desiliconization pyrolytic carbon that step (3) obtains is uniformly mixed with impregnating pitch, is placed in reaction
In kettle, other conditions are consistent with embodiment 3, obtain catalysis rice husk/asphaltic base capacitance carbon AC6.
Embodiment 7
Raw rice husk is sieved and is cleaned, it is 10mm~20mm to be crushed to grain size, and the HCl solution for being 2% with mass concentration is pressed
According to solid-to-liquid ratio 1Kg:10L is mixed, and other conditions are consistent with embodiment 3, obtains catalysis rice husk/asphaltic base capacitance carbon AC7.
Embodiment 8
(1) according to butt quality than 4:1, catalysis rice husk/asphaltic base capacitance carbon prepared by embodiment 3 is added to electrode drip
In green alcohol suspending liquid, it is dispersed with stirring 1h, heating recovery solvent, solid is placed in drying box, 85 DEG C of dry 5h~12h, is prepared
Go out pitch/capacitance carbon mixed-powder；
(2) pitch/capacitance carbon mixed-powder is transferred in tube furnace, under nitrogen protection, is warming up to 200 DEG C of constant temperature heatings
1h is handled, then is warming up to 800 DEG C of constant temperature heat treatment 1h, cooling breaks up, prepares asphalt modification capacitance carbon AC8.
The cyclical stability and specific capacitance of 1 embodiment sample of table
Note：Volumetric capacitance is tested in the KOH electrolyte of 6moL/L with cyclical stability.
As it can be seen from table 1 the volumetric capacitance of catalysis rice husk/asphaltic base capacitance carbon has compared with rice husk base capacitance carbon
Larger promotion, electrochemical cycle stability are also better.
Obviously, the explanation of above example is only intended to facilitating the understanding of the method and its core concept of the invention, but it is right
It, can be in the spirit for not departing from claims of the present invention and the case where principle for those skilled in the art
Under a variety of variations, modification carried out to these embodiments and replace, these improvement and modification also fall into the guarantor of the claims in the present invention
Within the scope of shield.
Claims (10)
1. the method for improving rice husk base capacitance carbon volumetric capacitance, which is characterized in that this method comprises the following steps：
It cleans Step 1: rice husk is sieved, crushes, obtain powdered rice hulls, powdered rice hulls carry out after being mixed with catalyst solution at dipping
Reason, after impregnation, is down to room temperature and is filtered, filter cake is placed at 80 DEG C~100 DEG C and is dried, and obtains pretreatment rice
Shell；
Step 2: the pretreatment rice husk prepared by step 1 is placed in tube furnace, 200 DEG C~300 DEG C are first warming up to, pyrolysis
0.5h, then be warming up to 500 DEG C~600 DEG C and be pyrolyzed 1h under nitrogen protection, it is down to room temperature, obtains pyrolytic carbon；
Step 3: pressing solid-to-liquid ratio 1Kg：The ratio of 10L is by the NaOH solution of the pyrolytic carbon obtained in step 2 and a concentration of 5wt%
It is added in reaction kettle, heating reflux reaction 2h, cools down, be separated by filtration, filter cake is washed till neutrality, dry, obtain desiliconization pyrolysis
Charcoal；
Step 4: the desiliconization pyrolytic carbon that step 3 obtains is uniformly mixed with impregnating pitch, it is placed in reaction kettle, is warming up to 150
DEG C~250 DEG C, 2h~5h is impregnated under conditions of pressure is 0.1MPa~0.6MPa obtains bituminizing presoma after cooling；
Step 5: the bituminizing presoma that step 4 obtains is transferred in tube furnace, it is warming up to 600 DEG C~1000 DEG C charings
1h~2h prepares bituminizing pyrolytic carbon；
Step 6: the bituminizing pyrolytic carbon prepared by step 5 is handled to obtain powdered carbon, powdered carbon is with alkali according to charcoal alkali ratio
1:(2.0~2.5) it is uniformly mixed, is placed in tube furnace, be first warming up to 450 DEG C with the heating rate of 5 DEG C/min, keep 0.5h,
It is further continued for being warming up to 700 DEG C with the heating rate of 5 DEG C/min, keeps 1h, taking-up is cooled to room temperature, in being washed till with hot deionized water
Property, in 120 DEG C of drying, prepare catalysis rice husk/asphaltic base capacitance carbon.
2. the method for improving rice husk base capacitance carbon volumetric capacitance, using as described in step 1 to step 6 in claim 1
Method, which is characterized in that further include：
Step 7: the preparation of asphalt modification capacitance carbon：
(1) catalysis rice husk/asphaltic base capacitance carbon prepared by step 6 is added in pitch suspension, be dispersed with stirring 0.5h~
2h, heating recovery solvent, solid are placed in drying box, and 85 DEG C of dry 5h~12h prepare pitch/capacitance carbon mixed-powder；
(2) pitch/capacitance carbon mixed-powder prepared by step (1) is transferred in tube furnace, under nitrogen protection, is warming up to
150 DEG C~250 DEG C constant temperature are heat-treated 1h~2h, then are warming up to 600 DEG C~1000 DEG C constant temperature heat treatment 1h~2h, and cooling is broken up,
Prepare asphalt modification capacitance carbon.
3. the method according to claim 1 or 2 for improving rice husk base capacitance carbon volumetric capacitance, it is characterised in that：Step
Impregnation process described in one is as follows：Reaction kettle is added in powdered rice hulls and catalyst solution, sealing is heated using steam,
Heating temperature is 120 DEG C~130 DEG C, impregnating by pressure 1h；Or the temperature of heating systems is 30 DEG C~50 DEG C, constant temperature impregnates for 24 hours.
4. the method according to claim 1 or 2 for improving rice husk base capacitance carbon volumetric capacitance, it is characterised in that：It is described
Catalyst in step 1 is NH4Cl、NH4OH、HCl、H2SO4、H3PO4One such or two kinds or more of mixture.
5. the method according to claim 1 or 2 for improving rice husk base capacitance carbon volumetric capacitance, it is characterised in that：It is described
The mass concentration of the catalyst solution of step 1 is 0%~20%.
6. the method according to claim 1 or 2 for improving rice husk base capacitance carbon volumetric capacitance, it is characterised in that：It is described
The powdered rice hulls of step 1 and the solid-to-liquid ratio of catalyst solution are 1Kg:(5~20) L.
7. the method according to claim 2 for improving rice husk base capacitance carbon volumetric capacitance, it is characterised in that：The step
The preparation method of pitch suspension in seven is：Asphalt powder is added in solvent, 0.5~2h is dispersed with stirring, it is outstanding to obtain pitch
Turbid.
8. the method according to claim 2 for improving rice husk base capacitance carbon volumetric capacitance, it is characterised in that：The step
The ratio of pitch and catalysis rice husk/asphaltic base capacitance carbon solid content is (10~30) in seven：100.
9. the method according to claim 2 for improving rice husk base capacitance carbon volumetric capacitance, it is characterised in that：Its feature exists
In：Solvent in the step 7 is one kind or two in cyclohexanol, absolute ethyl alcohol, acetone, tetrahydrofuran, hexamethylene, n-hexane
The mixture of kind.
10. the method for raising rice husk base capacitance carbon volumetric capacitance according to claim 8 or claim 9, it is characterised in that：It is described
The solid-to-liquid ratio of pitch and solvent is (5Kg~15Kg):100L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810807326.3A CN108726517B (en) | 2018-07-21 | 2018-07-21 | Method for improving volume specific capacitance of rice hull-based capacitance carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810807326.3A CN108726517B (en) | 2018-07-21 | 2018-07-21 | Method for improving volume specific capacitance of rice hull-based capacitance carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108726517A true CN108726517A (en) | 2018-11-02 |
| CN108726517B CN108726517B (en) | 2022-03-18 |
Family
ID=63927262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810807326.3A Active CN108726517B (en) | 2018-07-21 | 2018-07-21 | Method for improving volume specific capacitance of rice hull-based capacitance carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108726517B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142051A (en) * | 2020-08-24 | 2020-12-29 | 吉林大学 | Method for removing active functional groups on surface of capacitance carbon by chemical covering method |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5217657A (en) * | 1989-09-05 | 1993-06-08 | Engle Glen B | Method of making carbon-carbon composites |
| CN1769165A (en) * | 2004-11-04 | 2006-05-10 | 罗门哈斯公司 | Carbons useful in energy storage devices |
| CN101269811A (en) * | 2008-05-08 | 2008-09-24 | 华东理工大学 | Preparation method for high-carbon yield asphalt group spherical absorbent charcoal |
| JP4199028B2 (en) * | 2003-03-12 | 2008-12-17 | 株式会社クレハ | Method for producing powdered carbide |
| CN103427069A (en) * | 2012-05-19 | 2013-12-04 | 湖南省正源储能材料与器件研究所 | Lithium ion battery composite anode material and preparation thereof |
| CN103464100A (en) * | 2013-09-06 | 2013-12-25 | 济南圣泉集团股份有限公司 | Method for using plant acidolysis dregs for preparing active carbon absorption material used for recycling solvents |
| CN103618088A (en) * | 2013-11-21 | 2014-03-05 | 刘铁建 | Preparation method of graphite material of lithium ion battery |
| KR20150068557A (en) * | 2013-12-11 | 2015-06-22 | 재단법인 포항산업과학연구원 | Method for producing pellet-shaped porous carbon materials |
| CN107364863A (en) * | 2017-07-21 | 2017-11-21 | 吉林大学 | The preparation method of modified rice husk matrix activated carbon |
| CN108101044A (en) * | 2017-12-12 | 2018-06-01 | 谢金庚 | A kind of nanostructured graphitic carbon material and preparation method thereof, application |
| CN108190884A (en) * | 2018-01-30 | 2018-06-22 | 武汉科技大学 | A kind of method that multistage mesoporous activated carbon is prepared using leaf as template |
| CN108231423A (en) * | 2017-12-08 | 2018-06-29 | 上海奥威科技开发有限公司 | Lithium-ion capacitor negative material particle and preparation method thereof |
-
2018
- 2018-07-21 CN CN201810807326.3A patent/CN108726517B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5217657A (en) * | 1989-09-05 | 1993-06-08 | Engle Glen B | Method of making carbon-carbon composites |
| JP4199028B2 (en) * | 2003-03-12 | 2008-12-17 | 株式会社クレハ | Method for producing powdered carbide |
| CN1769165A (en) * | 2004-11-04 | 2006-05-10 | 罗门哈斯公司 | Carbons useful in energy storage devices |
| CN101269811A (en) * | 2008-05-08 | 2008-09-24 | 华东理工大学 | Preparation method for high-carbon yield asphalt group spherical absorbent charcoal |
| CN103427069A (en) * | 2012-05-19 | 2013-12-04 | 湖南省正源储能材料与器件研究所 | Lithium ion battery composite anode material and preparation thereof |
| CN103464100A (en) * | 2013-09-06 | 2013-12-25 | 济南圣泉集团股份有限公司 | Method for using plant acidolysis dregs for preparing active carbon absorption material used for recycling solvents |
| CN103618088A (en) * | 2013-11-21 | 2014-03-05 | 刘铁建 | Preparation method of graphite material of lithium ion battery |
| KR20150068557A (en) * | 2013-12-11 | 2015-06-22 | 재단법인 포항산업과학연구원 | Method for producing pellet-shaped porous carbon materials |
| CN107364863A (en) * | 2017-07-21 | 2017-11-21 | 吉林大学 | The preparation method of modified rice husk matrix activated carbon |
| CN108231423A (en) * | 2017-12-08 | 2018-06-29 | 上海奥威科技开发有限公司 | Lithium-ion capacitor negative material particle and preparation method thereof |
| CN108101044A (en) * | 2017-12-12 | 2018-06-01 | 谢金庚 | A kind of nanostructured graphitic carbon material and preparation method thereof, application |
| CN108190884A (en) * | 2018-01-30 | 2018-06-22 | 武汉科技大学 | A kind of method that multistage mesoporous activated carbon is prepared using leaf as template |
Non-Patent Citations (2)
| Title |
|---|
| OKHOVAT, A.: ""Pore Size Distribution Analysis of Coal-Based Activated Carbons: Investigating the Effects of Activating Agent and Chemical Ratio"", 《ISRN CHEMICAL ENGINEERING》 * |
| 刘艳华: ""沥青改性稻壳基活性炭的制备及电化学性能"", 《高等学校化学学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142051A (en) * | 2020-08-24 | 2020-12-29 | 吉林大学 | Method for removing active functional groups on surface of capacitance carbon by chemical covering method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108726517B (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108483442B (en) | Preparation method of nitrogen-doped carbon electrode material with high mesoporous rate | |
| Li et al. | Green conversion of bamboo chips into high-performance phenol adsorbent and supercapacitor electrodes by simultaneous activation and nitrogen doping | |
| CN109516458A (en) | A kind of biomass-based graded porous carbon and preparation method thereof | |
| CN109987604B (en) | Porous carbon material and preparation method thereof | |
| JP5400892B2 (en) | Method for producing porous activated carbon | |
| CN106115652B (en) | A kind of B and/or P, N codope perilla leaf porous carbon and preparation method thereof | |
| CN106365163B (en) | A kind of preparation method of sisal fiber activated carbon and the application of the sisal fiber activated carbon in lithium-ion capacitor | |
| CN108439402B (en) | A kind of supercapacitor ginger stalk matrix activated carbon and preparation method thereof | |
| CN107697913B (en) | Preparation method of walnut shell-based high-capacitance graded porous carbon | |
| CN105948041B (en) | A kind of fungi matrix activated carbon nanofiber and the preparation method and application thereof | |
| CN106348295A (en) | Preparation method of walnut shell active carbon | |
| CN106744951A (en) | A kind of quick method for preparing activated carbon | |
| CN102311113A (en) | Tobacco stalk based porous carbon material for electrodes of super capacitor and preparation method thereof | |
| CN105036110B (en) | Loose and porous structure Chinese alpine rush biological carbon and preparation method thereof | |
| JP2012507470A5 (en) | ||
| CN105645410B (en) | 3D network pore structure Supercapacitor carbons and preparation method thereof | |
| CN104715936B (en) | A kind of classifying porous carbon electrode material and preparation method for ultracapacitor | |
| CN106629723A (en) | Biomass-based N, S and P-containing co-doped porous carbon and application thereof | |
| CN109110756A (en) | Derivative carbon electrode material of a kind of homogeneous corncob and preparation method thereof | |
| CN107958797A (en) | A kind of preparation method of the biomass-based active carbon electrode material of highly basic ammonia co-activating | |
| CN108128773A (en) | A kind of method that electrode for electrochemical capacitor carbon material is prepared using peanut shell | |
| CN104803381B (en) | Hunan oil-tea camellia husks is utilized to prepare method and this activated carbon and the application thereof of activated carbon | |
| CN102867654A (en) | Graphitized activated carbon electrode material for supercapacitor and preparation method thereof | |
| CN113135568A (en) | Nitrogen-doped porous carbon material and preparation method and application thereof | |
| CN106915744A (en) | A kind of stalk resource Application way |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |