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 PDF

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CN109019598A
CN109019598A CN201810791662.3A CN201810791662A CN109019598A CN 109019598 A CN109019598 A CN 109019598A CN 201810791662 A CN201810791662 A CN 201810791662A CN 109019598 A CN109019598 A CN 109019598A
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porous carbon
carbon material
dimensional porous
biomass
specific capacitance
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刘应亮
余沛峰
梁业如
董汉武
胡航
郑明涛
肖勇
黄剑瑜
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South China Agricultural University
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South China Agricultural University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/30Active carbon
    • C01B32/312Preparation
    • C01B32/342Preparation characterised by non-gaseous activating agents
    • C01B32/348Metallic compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/30Active carbon
    • C01B32/312Preparation
    • C01B32/318Preparation characterised by the starting materials
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/30Active carbon
    • C01B32/312Preparation
    • C01B32/318Preparation characterised by the starting materials
    • C01B32/324Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/24Electrodes 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22Electrodes
    • H01G11/30Electrodes characterised by their material
    • H01G11/32Carbon-based
    • H01G11/44Raw materials therefor, e.g. resins or coal
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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

A kind of mixing biomass prepares the method and system of the three-dimensional porous carbon material of high specific capacitance At three-dimensional porous carbon material and its application
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.
CN201810791662.3A 2018-07-18 2018-07-18 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 Pending CN109019598A (en)

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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
CN112054188A (en) * 2020-09-15 2020-12-08 湖南大昊科技有限公司 Ion battery cathode material and preparation method and application thereof
CN113443626A (en) * 2020-03-26 2021-09-28 华东理工大学 Preparation method of mixed biomass activated carbon and application of mixed biomass activated carbon in super capacitor
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
CN114784298A (en) * 2022-03-21 2022-07-22 上海理工大学 Preparation method of porous carbon loaded metal organic framework ZIF-67 composite material
CN115206693A (en) * 2022-06-24 2022-10-18 四川金时新能科技有限公司 Biomass high-doping high-defect carbon material and preparation method and application thereof

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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
CN109482161A (en) * 2019-01-15 2019-03-19 广东省生物工程研究所(广州甘蔗糖业研究所) The modified bagasse graded porous carbon of two sections of amine of energy efficient absorption mercury and preparation method and application
CN109482161B (en) * 2019-01-15 2021-08-03 广东省生物工程研究所(广州甘蔗糖业研究所) Two-section amine modified bagasse hierarchical porous carbon capable of efficiently adsorbing mercury, and preparation method and application thereof
CN110706940B (en) * 2019-10-17 2021-09-28 福建工程学院 Three-dimensional porous carbon-manganese oxide core-shell structure material and preparation method and application thereof
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
CN113443626A (en) * 2020-03-26 2021-09-28 华东理工大学 Preparation method of mixed biomass activated carbon and application of mixed biomass activated carbon in super capacitor
CN112054188A (en) * 2020-09-15 2020-12-08 湖南大昊科技有限公司 Ion battery cathode material and preparation method and application thereof
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
CN114408919B (en) * 2022-02-09 2024-01-02 山东润生生物科技有限公司 Porous carbon material based on high-temperature thermal shock carbonization and KOH activation of coconut shell material, preparation method and application
CN114784298A (en) * 2022-03-21 2022-07-22 上海理工大学 Preparation method of porous carbon loaded metal organic framework ZIF-67 composite material
CN115206693A (en) * 2022-06-24 2022-10-18 四川金时新能科技有限公司 Biomass high-doping high-defect carbon material and preparation method and application thereof
CN115206693B (en) * 2022-06-24 2024-01-05 四川金时新能科技有限公司 Biomass high-doping high-defect carbon material and preparation method and application thereof

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