CN109019598A - A kind of mixing biomass prepares the method and manufactured three-dimensional porous carbon material and its application of the three-dimensional porous carbon material of high specific capacitance - Google Patents
A kind of mixing biomass prepares the method and manufactured three-dimensional porous carbon material and its application of the three-dimensional porous carbon material of high specific capacitance Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 65
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 59
- 238000002156 mixing Methods 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 19
- 235000013162 Cocos nucifera Nutrition 0.000 claims abstract description 26
- 244000060011 Cocos nucifera Species 0.000 claims abstract description 26
- 239000010903 husk Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000003763 carbonization Methods 0.000 claims abstract description 20
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 9
- 229920002472 Starch Polymers 0.000 claims abstract description 4
- 239000008103 glucose Substances 0.000 claims abstract description 4
- 239000008107 starch Substances 0.000 claims abstract description 4
- 235000019698 starch Nutrition 0.000 claims abstract description 4
- 239000005720 sucrose Substances 0.000 claims abstract description 4
- 239000010902 straw Substances 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 241000609240 Ambelania acida Species 0.000 claims description 13
- 239000010905 bagasse Substances 0.000 claims description 13
- 239000007772 electrode material Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- -1 bark Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000037452 priming Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002585 base Substances 0.000 abstract 8
- 239000001913 cellulose Substances 0.000 abstract 2
- 229920002678 cellulose Polymers 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 230000001351 cycling effect Effects 0.000 description 8
- 206010013786 Dry skin Diseases 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000003990 capacitor Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- 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
-
- 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
-
- 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
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- 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
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention belongs to the preparation technical field of biomass porous carbon, three-dimensional porous carbon material and manufactured three-dimensional porous carbon material and its application that a kind of mixing biomass prepares high specific capacitance are disclosed.The method that the present invention uses hydrothermal carbonization to combine with alkali metal hydroxide, prepares the porous carbon materials such as bagasse-coconut husk mixed base, coconut husk-sucrose mixed base, coconut husk-glucose mixed base, bagasse-cellulose mixed base, bagasse-bark mixed base, coconut husk-cornstalk mixed base, coconut husk-straw mixed base, starch and cellulose mixed base.The present invention has preparation method simple, and cost is relatively low；It superhigh specific surface area, high conductivity and three-dimensional porous combines；The advantages that excellent chemical property.
Description
Technical field
The invention belongs to the preparation technical fields of biomass porous carbon, and in particular to a kind of mixing biomass preparation is high than electricity
The three-dimensional porous carbon material and manufactured three-dimensional porous carbon material that hold and its application.
Background technique
In recent years, porous carbon materials achieve significant progress in the energy storages such as electrochemistry, absorption field.On the one hand,
The advantages that due to the from a wealth of sources, cheap and easy to get of biomass, abundance, the preparation of porous carbon materials has been widely used in it.
On the other hand, possess high-specific surface area (> 1800m2g-1) porous carbon materials due to more active site, can
Store more quantities of electric charge；And it can reduce the mass transfer impedance of electrolyte with three-dimensional porous structure；High conductivity is also advantageous
In the quick conduction of electronics, the energy density of supercapacitor is improved.Therefore high ratio of the biomass as precursor preparation is used
Surface area porous carbon material is the ideal material for supercapacitor.
Supercapacitor is mainly used in palm PC, electric network reconstruction, too as a kind of important electrochemical energy storing device
The civilian and military domains such as positive energy photovoltaic power generation, energy-conserving elevator, backup power source, new-energy automobile.As the whole world disappears for the energy
Consumption and the attention of environmental protection just need commercially viable to have both high quality specific capacitance (> 400F g-1) and excellent stable circulation
Property electrode material for super capacitor be used for extensive energy storage.The commercialized electrode material for super capacitor of present
Main or active carbon (such as YP-50 and CEP21KS), but be then mainly derived from as the presoma for preparing commercial activated carbons
The by-product of Petroleum Production, and petroleum is a kind of natural resources of non-sustainability, and exploitation, transport, refinement, the use of petroleum
Etc. processes also result in environmental pollution etc. harm.In these commercial activated carbons, YP-50 (Japanese Kuraray company) is due to answering
When for supercapacitor, there is excellent cyclical stability and be widely adopted.But its quality specific capacitance is only about
180F g-1, it is difficult to meet the needs of growing high specific capacitance electrode material.As supercapacitor high specific capacitance electrode material
The quality specific capacitance of the representative of material, CEP21KS (Power Carbon Technology company of South Korea) reaches 300F g-1, still
Its presoma source is pitch (petroleum by-products), and when being applied to supercapacitor, cyclical stability is insufficient.
In conclusion not having both superior quality specific capacitance (> 400F g still at present-1) and stable circulation performance and business it is living
The preparation method for the carbon material that property charcoal compares favourably.This also significantly limit supercapacitor in terms of answer
With.
Summary of the invention
In place of solving shortcoming and defect in the prior art, the primary purpose of the present invention is that providing a kind of mixing life
The method that substance prepares the three-dimensional porous carbon material of high specific capacitance.Different biomass is mixed first, is obtained through hydrothermal carbonization
Presoma is activated using KOH, and then the three-dimensional porous carbon of height ratio capacity, excellent cycling stability is realized by synergistic effect
The preparation of material.
Another object of the present invention is to provide the three-dimensional porous carbon materials that a kind of above method is prepared.
A further object of the present invention is to provide a kind of applications of above-mentioned three-dimensional porous carbon material.
The object of the invention is achieved through the following technical solutions:
A kind of method that mixing biomass prepares the three-dimensional porous carbon material of high specific capacitance, comprising the following steps:
(1) after mixing pretreated biomass, hydrothermal carbonization reaction, the mixing biomass forerunner being carbonized are carried out
Body；
(2) the mixing biomass presoma of carbonization is mixed with alkali metal hydroxide, is activated under an inert atmosphere
Reaction, obtains the three-dimensional porous carbon material of high specific capacitance.
Step (1) biomass be coconut husk, bagasse, bark, starch, glucose, sucrose, cellulose powder, straw and
It is two or more in cornstalk.
Step (1) the pretreated biomass is that biomass is dry and crushing obtains fine powder of the partial size less than 75 μm,
Then 200 mesh test sieves are crossed.
Step (1) mixing is to mix two kinds of pretreated biomass for 5:1~1:10 proportion according to mass ratio；Institute
The temperature for stating hydrothermal carbonization reaction is 60~500 DEG C, and the time is 0.5~36h.
Step (1) mixing is to mix two kinds of pretreated biomass for 3:1~1:3 proportion according to mass ratio；Institute
The temperature for stating hydrothermal carbonization reaction is 180 DEG C, time 12h.
Step (1) mixing is to mix two kinds of pretreated biomass for 1:1 proportion according to mass ratio.
Step (2) alkali metal hydroxide is one or both of potassium hydroxide and sodium hydroxide；The carbonization
Mixing biomass presoma and alkali metal hydroxide mass ratio be 2:1~1:6；The temperature of the priming reaction is 700
~800 DEG C, the time is 2~3h.
The mixing biomass presoma of step (2) described carbonization and the mass ratio of alkali metal hydroxide are 1:4.
The three-dimensional porous carbon material for the high specific capacitance that above-mentioned method is prepared, the ratio electricity of the three-dimensional porous carbon material
Appearance reaches 442F g-1。
The three-dimensional porous carbon material of above-mentioned high specific capacitance is in preparation supercapacitor, lithium ion battery or sodium-ion battery
Electrode material in application.
Commercial activated carbons YP-50 is 180F g at present-1, specific capacity conservation rate is 83%, the specific volume of another CEP21KS
Amount is 300F g-1, but specific capacity conservation rate is 73%, and the present invention passes through the three-dimensional porous carbon material specific capacitance being mixed with
Above 400F g-1, and specific capacitance conservation rate can achieve 72% or so, and the cycle performance of additional embodiment 1 tests also table
Bright cyclical stability is close to current commercial activated carbons, so comprehensive performance is better than commercial activated carbons.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) present invention is combined the advantages of different biomass by acting synergistically, and passes through the different of optimization biomass
Mixed proportion achievees the effect that 1+1 > 2, can prepare the carbon material that height ratio capacity and excellent cyclical stability combine.
(2) porous carbon materials prepared by the present invention are due to specific surface area with higher, high conductivity and three-dimensional porous knot
Structure can be used as the electrode material of preferable super capacitor, in 0.5~50A g-1Constant current charge-discharge survey is carried out under current density
Examination, can be obtained highest 441F g-1Specific capacitance, even if in 50A g-1High current density under, still have 309F g-1Ratio electricity
Hold.
(3) preparation method of the present invention is simple, and cost is relatively low, is suitable for industrialization.
Detailed description of the invention
Fig. 1 is in embodiment 1 using bagasse as the scanning electron microscope (SEM) photograph of the made sample of raw material.
Fig. 2 is in embodiment 1 using coconut husk as the scanning electron microscope (SEM) photograph of the made sample of raw material.
Fig. 3 is in embodiment 1 with the scanning electron microscope (SEM) photograph of the made sample of mixing biomass presoma of carbonization.
Fig. 4 is in embodiment 1 with the adsorption isothermal curve of the made sample of mixing biomass presoma of carbonization and aperture point
Cloth curve graph.
Fig. 5 is in embodiment 1 using the made sample of mixing biomass presoma of carbonization as electrode material for super capacitor
(the 5mV s under different scanning speed-1、10mV s-1 20mV s-1、50mV s-1、100mV s-1With 200mV s-1) circulation volt
Pacify curve.
Fig. 6 is in embodiment 1 using the made sample of mixing biomass presoma of carbonization as electrode material for super capacitor
(the 0.5A g under different current densities-1、1A g-1、2A g-1、5A g-1、10A g-1、20A g-1、30A g-1、40A g-1With
50A g-1) constant current charge-discharge curve.
Fig. 7 is in embodiment 1 using the made sample of mixing biomass presoma of carbonization as electrode material for super capacitor
The specific capacitance change curve under different current densities.
Fig. 8 be the made sample of mixing biomass presoma in embodiment 1 using carbonization as electrode material in 20A g-1's
Under the conditions of recycle 20000 specific capacitances and keep figure.
Specific implementation method
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
The present embodiment provides high specific capacitances, the three-dimensional porous carbon material of excellent cycling stability and preparation method thereof, including
Following steps:
(1) 100g bagasse and 100g coconut husk are recycled pulverizer to crush, cross 200 mesh test sieves in 105 DEG C of dryings,
Obtain pretreated bagasse and coconut husk；
(2) the pretreated bagasse of 1g and the pretreated coconut husk of 1g are weighed in polytetrafluoroethyllining lining, adds 20ml
Water stirs evenly, then it is enclosed within 180 DEG C of reaction 12h in baking oven with reaction kettle, filters, before the mixing biomass being carbonized
Drive body；
(3) it weighs 4g KOH and is uniformly mixed in mortar with the mixing biomass presoma that 1g is carbonized, then mixture is turned
It moves on to and is subsequently placed into tube furnace in nickel crucible, be 70ml min in flow velocity-1Nitrogen atmosphere under, with 5 DEG C of min-1Speed be raised to
700 DEG C, 2h is kept the temperature, later to be naturally cooling to room temperature, by the 2mol L of the product after reaction-1Hydrochloric acid solution cleaning, after spend
Ionized water is cleaned to neutrality, dries 3h in 105 DEG C of baking ovens then to get the three-dimensional porous carbon material of high specific capacitance is arrived.
The pretreated bagasse of 2g is weighed in step (2) in polytetrafluoroethyllining lining, is added 20ml water and is stirred evenly,
Then subsequent step is carried out, the scanning figure of last resulting carbon material is as shown in Figure 1；
The pretreated coconut husk of 2g is weighed in step (2) in polytetrafluoroethyllining lining, is added 20ml water and is stirred evenly, so
After carry out subsequent step, the scanning figure of last resulting carbon material is as shown in Figure 2；
The scanning figure of the carbon material of the present embodiment mixing biomass preparation is as shown in figure 3, carbon materials prepared by mixing biomass
The N of material2Adsorption desorption curve as shown in figure 4, mixing biomass preparation carbon material three-electrode system cyclic voltammetry knot
Fruit as shown in figure 5, the instant potential test result of the three-electrode system of the carbon material of mixing biomass preparation as shown in fig. 6, mixed
The specific capacitance conservation rate curve of the three-electrode system of the carbon material of symphysis substance preparation is as shown in fig. 7, prepared by mixing biomass
Test results are shown in figure 8 for the cycle performance of the three-electrode system of carbon material.
Embodiment 2
The present embodiment provides a kind of high specific capacitance, the three-dimensional porous carbon material of excellent cycling stability and preparation method thereof,
The following steps are included:
(1) 100g bagasse and 100g coconut husk are recycled pulverizer to crush, cross 200 mesh test sieves in 105 DEG C of dryings,
Obtain pretreated bagasse and coconut husk；
(2) the pretreated bagasse of 1.33g and the pretreated coconut husk of 0.67g are weighed in polytetrafluoroethyllining lining, then plus
Enter 20ml water to stir evenly, then it is enclosed within 180 DEG C of reaction 12h in baking oven with reaction kettle, filter, the mixing being carbonized is raw
Substance presoma；
(4) it weighs 4g KOH and is uniformly mixed in mortar with the mixing biomass presoma that 1g is carbonized, then mixture is turned
It moves on to and is subsequently placed into tube furnace in nickel crucible, be 70ml min in flow velocity-1Nitrogen atmosphere under, with 5 DEG C of min-1Speed be raised to
700 DEG C, 2h is kept the temperature, later to be naturally cooling to room temperature, by the 2mol L of the product after reaction-1Hydrochloric acid solution cleaning, after spend
Ionized water is cleaned to neutrality, dries 3h in 105 DEG C of baking ovens then to get being 426F g to specific capacitance-1, specific capacity conservation rate is
73% three-dimensional porous carbon material.
Embodiment 3
The present embodiment provides a kind of high specific capacitance, the three-dimensional porous carbon material of excellent cycling stability and preparation method thereof,
The following steps are included:
(1) it recycles pulverizer to crush in 105 DEG C of dryings 100g bagasse, crosses 200 mesh test sieves, pre-processed
Bagasse；
(2) the pretreated bagasse of 1.5g and 0.5g hemicellulose powder are weighed in polytetrafluoroethyllining lining, is added
20ml water stirs evenly, then it is enclosed within 180 DEG C of reaction 12h in baking oven with reaction kettle, filters, the mixed biologic being carbonized
Matter presoma；
(3) it weighs 4g KOH and is uniformly mixed in mortar with the mixing biomass presoma that 1g is carbonized, then mixture is turned
It moves on to and is subsequently placed into tube furnace in nickel crucible, be 70ml min in flow velocity-1Nitrogen atmosphere under, with 5 DEG C of min-1Speed be raised to
700 DEG C, 2h is kept the temperature, later to be naturally cooling to room temperature, by the 2mol L of the product after reaction-1Hydrochloric acid solution cleaning, after spend
Ionized water is cleaned to neutrality, dries 3h in 105 DEG C of baking ovens then to get being 419F g to specific capacitance-1, specific capacity conservation rate is
71% three-dimensional porous carbon material.
Embodiment 4
The present embodiment provides a kind of high specific capacitance, the three-dimensional porous carbon material of excellent cycling stability and preparation method thereof,
The following steps are included:
(1) it recycles pulverizer to crush in 105 DEG C of dryings 100g coconut husk, crosses 200 mesh test sieves, obtain pretreated
Coconut husk；
(2) the pretreated coconut husk of 1g and 1g glucose are weighed in polytetrafluoroethyllining lining, it is equal to add the stirring of 20ml water
It is even, then it is enclosed within 180 DEG C of reaction 12h in baking oven with reaction kettle, it filters, the mixing biomass presoma being carbonized；
(3) it weighs 4g KOH and is uniformly mixed in mortar with the mixing biomass presoma that 1g is carbonized, then mixture is turned
It moves on to and is subsequently placed into tube furnace in nickel crucible, be 70ml min in flow velocity-1Nitrogen atmosphere under, with 5 DEG C of min-1Speed be raised to
700 DEG C, 2h is kept the temperature, later to be naturally cooling to room temperature, by the 2mol L of the product after reaction-1Hydrochloric acid solution cleaning, after spend
Ionized water is cleaned to neutrality, dries 3h in 105 DEG C of baking ovens then to get being 402F g to specific capacitance-1, specific capacity conservation rate is
73% three-dimensional porous carbon material.
Embodiment 5
The present embodiment provides a kind of high specific capacitance, the three-dimensional porous carbon material of excellent cycling stability and preparation method thereof,
The following steps are included:
(1) it recycles pulverizer to crush in 105 DEG C of dryings 100g coconut husk, crosses 200 mesh test sieves, obtain pretreated
Coconut husk；
(2) the pretreated coconut husk of 1g and 1g sucrose are weighed in polytetrafluoroethyllining lining, 20ml water is added and stirs evenly,
It is enclosed within 180 DEG C of reaction 12h in baking oven with reaction kettle again, is filtered, the mixing biomass presoma being carbonized；
(3) it weighs 4g KOH and is uniformly mixed in mortar with the mixing biomass presoma that 1g is carbonized, then mixture is turned
It moves on to and is subsequently placed into tube furnace in nickel crucible, be 70ml min in flow velocity-1Nitrogen atmosphere under, with 5 DEG C of min-1Speed be raised to
700 DEG C, 2h is kept the temperature, later to be naturally cooling to room temperature, by the 2mol L of the product after reaction-1Hydrochloric acid solution cleaning, after spend
Ionized water is cleaned to neutrality, dries 3h in 105 DEG C of baking ovens then to get being 443F g to specific capacitance-1, specific capacity conservation rate is
69% three-dimensional porous carbon material.
Embodiment 6
The present embodiment provides a kind of high specific capacitance, the three-dimensional porous carbon material of excellent cycling stability and preparation method thereof,
The following steps are included:
(1) it recycles pulverizer to crush in 105 DEG C of dryings 100g coconut husk, crosses 200 mesh test sieves, obtain pretreated
Coconut husk；
(2) 1g soluble starch and 1g coconut husk are weighed in polytetrafluoroethyllining lining, 20ml water is added and stirs evenly, then
It is enclosed within 180 DEG C of reaction 12h in baking oven with reaction kettle, is filtered, the mixing biomass presoma being carbonized；
(3) it weighs 4g KOH and is uniformly mixed in mortar with the mixing biomass presoma that 1g is carbonized, then mixture is turned
It moves on to and is subsequently placed into tube furnace in nickel crucible, be 70ml min in flow velocity-1Nitrogen atmosphere under, with 5 DEG C of min-1Speed be raised to
700 DEG C, 2h is kept the temperature, later to be naturally cooling to room temperature, by the 2mol L of the product after reaction-1Hydrochloric acid solution cleaning, after spend
Ionized water is cleaned to neutrality, dries 3h in 105 DEG C of baking ovens then to get being 452F g to specific capacitance-1, specific capacity conservation rate is
76% three-dimensional porous carbon material.
Embodiment 7
The present embodiment provides a kind of high specific capacitance, the three-dimensional porous carbon material of excellent cycling stability and preparation method thereof,
The following steps are included:
(1) it recycles pulverizer to crush in 105 DEG C of dryings 100g coconut husk, crosses 200 mesh test sieves, obtain pretreated
Coconut husk；
(2) 1g cellulose acetate and the pretreated coconut husk of 1g are weighed in polytetrafluoroethyllining lining, 20ml water is added and stirs
It mixes uniformly, then it is enclosed within 180 DEG C of reaction 12h in baking oven with reaction kettle, filter, the mixing biomass forerunner being carbonized
Body；
(3) it weighs 4g KOH and is uniformly mixed in mortar with the mixing biomass presoma that 1g is carbonized, then mixture is turned
It moves on to and is subsequently placed into tube furnace in nickel crucible, be 70ml min in flow velocity-1Nitrogen atmosphere under, with 5 DEG C of min-1Speed be raised to
700 DEG C, 2h is kept the temperature, later to be naturally cooling to room temperature, by the 2mol L of the product after reaction-1Hydrochloric acid solution cleaning, after spend
Ionized water is cleaned to neutrality, dries 3h in 105 DEG C of baking ovens then to get being 418F g to specific capacitance-1, specific capacity conservation rate is
74% three-dimensional porous carbon material.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of method that mixing biomass prepares the three-dimensional porous carbon material of high specific capacitance, it is characterised in that including following step
It is rapid:
(1) after mixing pretreated biomass, hydrothermal carbonization reaction, the mixing biomass presoma being carbonized are carried out；
(2) the mixing biomass presoma of carbonization is mixed with alkali metal hydroxide, carries out priming reaction under an inert atmosphere,
Obtain the three-dimensional porous carbon material of high specific capacitance.
2. the method that a kind of mixing biomass according to claim 1 prepares the three-dimensional porous carbon material of high specific capacitance,
Be characterized in that: step (1) biomass be coconut husk, bagasse, bark, starch, glucose, sucrose, cellulose powder, straw and
It is two or more in cornstalk.
3. the method that a kind of mixing biomass according to claim 1 prepares the three-dimensional porous carbon material of high specific capacitance,
Be characterized in that: step (1) the pretreated biomass is that biomass is dry and crushing obtains fine powder of the partial size less than 75 μm,
Then 200 mesh test sieves are crossed.
4. the method that a kind of mixing biomass according to claim 1 prepares the three-dimensional porous carbon material of high specific capacitance,
Be characterized in that: step (1) mixing is to mix two kinds of pretreated biomass for 5:1~1:10 proportion according to mass ratio；
The temperature of the hydrothermal carbonization reaction is 60~500 DEG C, and the time is 0.5~36h.
5. the method that a kind of mixing biomass according to claim 1 prepares the three-dimensional porous carbon material of high specific capacitance,
Be characterized in that: step (1) mixing is to mix two kinds of pretreated biomass for 3:1~1:3 proportion according to mass ratio；Institute
The temperature for stating hydrothermal carbonization reaction is 180 DEG C, time 12h.
6. the method that a kind of mixing biomass according to claim 1 prepares the three-dimensional porous carbon material of high specific capacitance,
Be characterized in that: step (1) mixing is to mix two kinds of pretreated biomass for 1:1 proportion according to mass ratio.
7. the method that a kind of mixing biomass according to claim 1 prepares the three-dimensional porous carbon material of high specific capacitance,
Be characterized in that: step (2) alkali metal hydroxide is one or both of potassium hydroxide and sodium hydroxide；The carbonization
Mixing biomass presoma and alkali metal hydroxide mass ratio be 2:1~1:6；The temperature of the priming reaction is 700
~800 DEG C, the time is 2~3h.
8. the method that a kind of mixing biomass according to claim 1 prepares the three-dimensional porous carbon material of high specific capacitance,
Be characterized in that: the mass ratio of the mixing biomass presoma of step (2) described carbonization and alkali metal hydroxide is 1:4.
9. the three-dimensional porous carbon material for the high specific capacitance that method according to claim 1-8 is prepared, special
Sign is: the specific capacitance of the three-dimensional porous carbon material reaches 442Fg-1。
10. the three-dimensional porous carbon material of high specific capacitance according to claim 9 is in preparation supercapacitor, lithium ion battery
Or the application in the electrode material of sodium-ion battery.
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| CN109809402A (en) * | 2019-01-14 | 2019-05-28 | 陕西科技大学 | A kind of preparation method being used for sodium-ion battery material with three-dimensional hollow porous carbon made of pomace |
| CN110706940A (en) * | 2019-10-17 | 2020-01-17 | 福建工程学院 | Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof |
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| CN112054188B (en) * | 2020-09-15 | 2023-03-24 | 湖南大昊科技有限公司 | Negative electrode material of ion battery and preparation method and application thereof |
| CN114408919A (en) * | 2022-02-09 | 2022-04-29 | 山东润生生物科技有限公司 | Coconut shell material-based porous carbon material subjected to high-temperature thermal shock carbonization and KOH activation, and preparation method and application thereof |
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