CN110482545B - Preparation method and application of high-crosslinking-degree starch - Google Patents

Preparation method and application of high-crosslinking-degree starch Download PDF

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CN110482545B
CN110482545B CN201910833492.5A CN201910833492A CN110482545B CN 110482545 B CN110482545 B CN 110482545B CN 201910833492 A CN201910833492 A CN 201910833492A CN 110482545 B CN110482545 B CN 110482545B
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starch
crosslinking
activated carbon
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CN110482545A (en
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陈成猛
孙国华
姚锦龙
孔庆强
朱庆华
石久龙
朱华
宋林刚
张超
马帅
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Shanxi Institute of Coal Chemistry of CAS
Shanxi Meijin Energy Co Ltd
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Shanxi Institute of Coal Chemistry of CAS
Shanxi Meijin Energy Co Ltd
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    • C—CHEMISTRY; METALLURGY
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    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • 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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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

The invention relates to a preparation method and application of starch with high crosslinking degree, belongs to the technical field of preparation of starch-based super capacitor activated carbon, and solves the technical problems that in the prior art, the starch has low crosslinking degree and is easy to generate a hollow structure after carbonization. The solution comprises the following steps: uniformly mixing starch, a cross-linking agent and deionized water in a closed stirring kettle, then pressurizing and stirring for a certain time at a certain temperature, finally drying to obtain composite starch, and carbonizing, activating and purifying to obtain the super-capacitor activated carbon. The method can eliminate the hollow structure formed by the composite starch in the carbonization process, prepare the compact sphere-like super-capacitor activated carbon, improve the tap density and the compacted density of the compact sphere-like super-capacitor activated carbon, and is beneficial to obtaining the super-capacitor with high energy density.

Description

Preparation method and application of high-crosslinking-degree starch
Technical Field
The invention belongs to the technical field of preparation of starch-based super-capacitor activated carbon, and particularly relates to a preparation method and application of starch with high crosslinking degree.
Background
The super-capacitor activated carbon is a high-end activated carbon, has the characteristics of super-large specific surface area, high purity, high specific capacitance and the like, and is used as a key electrode material for a super-capacitor. Currently, the commercialized super capacitor activated carbon mainly adopts coconut shells or petroleum coke as a raw material, and is finally crushed into a certain particle size after being treated by the processes of carbonization, activation and the like. The crushed activated carbon is generally in an irregular shape and has a lower tap density, so that the prepared capacitor pole piece has a lower compaction density. With the development of downstream markets, higher requirements are made on the energy density of the supercapacitor. The performance of the conventional super-capacitor activated carbon reaches the limit and cannot be continuously improved.
Starch is a renewable resource with wide sources, and can be prepared into sphere-like super-capacitor activated carbon through processes of crosslinking, carbonization, activation and the like, which is very favorable for improving the compaction density of the pole piece. However, starch granules are compact, and conventional crosslinking technology can only make molecular chains on the surface react with a crosslinking agent, and the internal molecular chains are difficult to fully crosslink. After carbonization treatment, molecular chains are seriously decomposed due to insufficient crosslinking inside starch granules, so that a cavity is formed, and finally the hollow capacitance activated carbon is obtained. The compacted density of the coated pole piece is still low, and the energy density of the capacitor is difficult to improve. In addition, in the charging and discharging process, the electrode solution easily permeates into a cavity inside the super-capacitor activated carbon, so that the electrolyte in the system is reduced, and the electrochemical performance of the super-capacitor activated carbon is influenced.
The method comprises the steps of carbonizing starch-based biomass carbon disclosed by Liu-En-Hui et al (publication No. CN 107043109A) at low temperature, purifying to remove impurities, uniformly mixing with an alkali solution, drying, calcining in air, activating, purifying and drying to obtain the super-capacitor activated carbon, wherein when the final product activated carbon is used as a capacitor electrode material, the compaction density is low, and the energy density of a capacitor is low.
(iv) subjecting the spray-dried starch to temperature-raising treatment under inert atmosphere to obtain starch-based carbon microspheres having a primary pore structure; grinding starch-based carbon microspheres, uniformly mixing with an activating agent, and heating and activating under an inert atmosphere; and introducing oxidizing gas, heating for activation, cooling, taking out to obtain a starch-based activated carbon microsphere crude product, washing the starch-based activated carbon microsphere crude product to be neutral, and drying to obtain spherical activated carbon with low ash flying content. The final product has a serious hollow structure and low compaction density.
Starch is a micron-sized spherical particle with a sphere-like structure, and the surface is compact. Generally, the cross-linking agent can only cross-link on the surface of the starch granule, but is difficult to penetrate into the granule, so that a hollow structure is formed in the subsequent carbonization and activation processes.
Disclosure of Invention
The invention provides a preparation method of high-crosslinking-degree starch and application thereof, aiming at overcoming the defects in the prior art and solving the technical problems that the starch in the prior art is low in crosslinking degree and is easy to generate a hollow structure after carbonization.
The design concept of the invention is as follows: the starch is subjected to micro-swelling in a certain temperature range, and the cross-linking agent is pressurized and impregnated into the starch granules while the shape of the starch granules is maintained, so that the starch granules are uniformly cross-linked, the cross-linking degree of the starch is improved, the hollow structure of a final product is avoided, and the aim of high tap density of the super-capacitor activated carbon is fulfilled.
The invention is realized by the following technical scheme.
A preparation method of high-crosslinking-degree starch comprises the following steps:
s1, adding starch, a cross-linking agent and deionized water into a closed reaction kettle in proportion, and stirring for 0.5-1h at the rotating speed of 40-500rpm to uniformly mix the raw materials to prepare starch slurry; wherein the mass ratio of the starch to the cross-linking agent to the deionized water is 1.15 to 1;
s2, heating the starch slurry prepared in the step S1 to 40-60 ℃ at a heating rate of 3-10 ℃/min, and stirring at a constant speed of 40-500rpm for 0.5-1h;
s3, filling inert gas into the reaction kettle until the pressure in the reaction kettle is 0.2-5MPa, and continuously stirring for 0.5-6h;
and S4, after stirring is finished, spray drying the reaction solution at 150-170 ℃ to obtain dry composite high-crosslinking-degree starch.
Further, in the step S1, the starch is one or more of potato starch, corn starch and wheat starch.
Further, in the step S1, the crosslinking agent is one or a combination of more of epichlorohydrin, phosphorus oxychloride, sodium trimetaphosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.
Further, in the step S3, the inert gas is one or a combination of nitrogen, argon and helium.
The preparation method of the high crosslinking degree starch comprises the steps of crosslinking the prepared dry composite high crosslinking degree starch for 0.5-10h at 120-220 ℃ under the protection of inert gas, and then carbonizing, activating and purifying to obtain the super-capacitor activated carbon.
Furthermore, the super-capacitor activated carbon is of a solid structure, the crosslinking degree is 60-80%, and the tap density is 0.45-0.65g/ml.
The invention has the following beneficial effects:
in the invention, the volume of the starch granules slightly expands in the reaction process of the mixed solution at the temperature of 40-60 ℃, and the cross-linking agent can smoothly diffuse into the starch granules under high pressure, so that the starch granules are fully cross-linked inside and outside, the breakage of molecular chains is reduced in the carbonization process, and a compact carbon network structure is formed, thereby avoiding the formation of a hollow structure, and finally obtaining the sphere-like super-capacitor activated carbon with high tap density.
Drawings
FIG. 1 is a scanning electron microscope microscopic morphology image of the capacitive carbon prepared in example 1.
FIG. 2 is a SEM micrograph of capacitive carbon prepared according to a comparative example corresponding to example 1.
FIG. 3 is a SEM micrograph of the capacitive carbon prepared in example 2.
FIG. 4 is a SEM micrograph of capacitive carbon prepared according to the comparative example of example 2.
FIG. 5 is a SEM micrograph of the capacitive carbon prepared in example 3.
FIG. 6 is a SEM micrograph of capacitive carbon prepared according to a comparative example corresponding to example 3.
FIG. 7 is a SEM micrograph of the capacitive carbon prepared in example 4.
FIG. 8 is a SEM micrograph of capacitive carbon prepared according to the comparative example of example 4.
FIG. 9 is a SEM micrograph of capacitive carbon prepared according to example 5.
FIG. 10 is a SEM micrograph of capacitive carbon prepared according to comparative example shown in example 5.
FIG. 11 is a SEM micrograph of capacitive carbon prepared according to example 6.
FIG. 12 is a SEM micrograph of capacitive carbon prepared according to comparative example of example 6.
FIG. 13 is a SEM micrograph of the capacitive carbon prepared in example 7.
FIG. 14 is a SEM micrograph of capacitive carbon prepared according to example 7 and corresponding to a comparative example.
FIG. 15 is a SEM micrograph of capacitive carbon prepared according to example 8.
FIG. 16 is a SEM micrograph of capacitive carbon prepared according to the comparative example of example 8.
FIG. 17 is a SEM micrograph of the capacitive carbon prepared in example 9.
FIG. 18 is a SEM micrograph of capacitive carbon prepared according to a comparative example corresponding to example 9.
FIG. 19 is a SEM micrograph of the capacitive carbon prepared in example 10.
FIG. 20 is a SEM micrograph of capacitive carbon prepared according to a comparative example corresponding to example 10.
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
The first embodiment is as follows:
1kg of potato starch, 1kg of phosphorus oxychloride and 4kg of deionized water are added into a closed reaction kettle and stirred for 0.7h at 100rpm, so that the materials are uniformly mixed. The starch slurry is heated to 50 ℃ at the heating rate of 7 ℃/min, and is continuously stirred for 0.7h at the speed of 100 rpm. Introducing nitrogen into the reaction kettle to ensure that the pressure in the kettle reaches 1MPa, and continuously stirring for 0.5h. And after stirring, spray drying the reaction solution at 160 ℃ to obtain dry composite starch, crosslinking for 0.5h at 200 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. The TEM image of the activated carbon obtained by the method and under normal temperature and pressure is shown in FIG. 1. The degree of crosslinking and tap density of the two are shown in the attached table.
Comparative example:
1kg of potato starch, 1kg of phosphorus oxychloride and 4kg of deionized water are added into a closed reaction kettle and stirred uniformly at 100rpm, and stirring is continued for 0.5h. And after stirring, drying the reaction solution to obtain composite starch, crosslinking for 0.5h (the crosslinking degree is 70%) at 200 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. (the same process route is used in the following examples)
Example two:
1kg of wheat starch, 0.2kg of ammonium dihydrogen phosphate and 1.6kg of deionized water are added into a closed reaction kettle and stirred for 0.5h at 300rpm, so that the wheat starch, the ammonium dihydrogen phosphate and the deionized water are uniformly mixed. The starch slurry is heated to 40 ℃ at the heating rate of 3 ℃/min, and is continuously stirred for 0.5h at the speed of 300 rpm. Introducing helium into the reaction kettle to ensure that the pressure in the reaction kettle reaches 5MPa, and continuously stirring for 4 hours. And after stirring, spray drying the reaction solution at 170 ℃ to obtain dry composite starch, crosslinking for 10 hours at 120 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. A TEM image of the activated carbon obtained by this method under normal temperature and pressure is shown in fig. 3. The degree of crosslinking and tap density of the two are shown in the attached table.
Example three:
1kg of a mixture of wheat starch and corn starch (the mass ratio of the wheat starch to the corn starch is 1. The starch slurry is heated to 60 ℃ at the heating rate of 10 ℃/min, and is continuously stirred for 0.5h at the speed of 60 rpm. Introducing argon into the reaction kettle to ensure that the pressure in the reaction kettle reaches 5MPa, and continuously stirring for 3 hours. And after stirring, spray-drying the reaction solution at 150 ℃ to obtain dry composite starch, crosslinking for 5 hours at 150 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. The TEM image of the activated carbon obtained by this method and under normal temperature and pressure is shown in FIG. 5. The degree of crosslinking and tap density of the two are shown in the attached table.
Example four:
1kg of a mixture of potato starch and corn starch (the mass ratio of the two is 2. The starch slurry is heated to 53 ℃ at the heating rate of 4 ℃/min, and is continuously stirred for 0.5h at the speed of 500 rpm. Introducing nitrogen into the reaction kettle to ensure that the pressure in the kettle reaches 2MPa, and continuously stirring for 2.5h. After stirring, spray drying the reaction solution at 165 ℃ to obtain dry composite starch, crosslinking for 4 hours at 180 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid super-capacitor activated carbon. A TEM image of the activated carbon obtained by this method under normal temperature and pressure is shown in fig. 7. The degree of crosslinking and tap density of the two are shown in the attached table.
Example five:
1kg of a mixture of wheat starch and potato starch (the mass ratio of the wheat starch to the potato starch is 1. The starch slurry was warmed to 45 ℃ at a rate of 10 ℃/min and stirred for 1h at 40 rpm. Introducing helium into the reaction kettle to ensure that the pressure in the reaction kettle reaches 0.2MPa, and continuously stirring for 6 hours. And after stirring, spray-drying the reaction solution at 155 ℃ to obtain dry composite starch, crosslinking for 8 hours at 140 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. A TEM image of the activated carbon obtained by this method under normal temperature and pressure is shown in fig. 9. The degree of crosslinking and tap density of the two are shown in the attached table.
Example six:
1kg of corn starch, 0.3kg of a mixture of sodium trimetaphosphate and ammonium dihydrogen phosphate (the mass ratio of the two is 1. The starch slurry is heated to 55 ℃ at the heating rate of 8 ℃/min, and is continuously stirred for 0.6h at the speed of 420 rpm. Introducing nitrogen and argon into the reaction kettle to ensure that the pressure in the reaction kettle reaches 1.5MPa, and continuously stirring for 3.5h. After stirring, spray drying the reaction solution at 167 ℃ to obtain dry composite starch, crosslinking for 4.5 h at 175 ℃ under the protection of nitrogen and helium, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. A TEM image of the activated carbon obtained by this method under normal temperature and pressure is shown in fig. 11. The degree of crosslinking and tap density of the two are shown in the attached table.
Example seven:
1kg of potato starch, 0.23kg of a mixture of diammonium hydrogen phosphate and phosphorus oxychloride (the mass ratio of the two is 1. The starch slurry is heated to 48 ℃ at the heating rate of 9 ℃/min, and is continuously stirred for 0.7h at the speed of 350 rpm. And introducing nitrogen into the reaction kettle to ensure that the pressure in the kettle reaches 3.5MPa, and continuously stirring for 2.7 hours. After stirring, spray drying the reaction solution at 152 ℃ to obtain dry composite starch, crosslinking for 7.5 h at 135 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid super-capacitor activated carbon. A TEM image of the activated carbon obtained by this method and under normal temperature and pressure is shown in fig. 13. The degree of crosslinking and tap density of the two are shown in the attached table.
Example eight:
1kg of a mixture of wheat starch and potato starch (the mass ratio of the wheat starch to the potato starch is 1.5), 0.5kg of phosphorus oxychloride and 3kg of deionized water are added into a closed reaction kettle and stirred for 0.6h at 150rpm, so that the materials are uniformly mixed. The starch slurry is heated to 58 ℃ at the heating rate of 4 ℃/min, and is continuously stirred for 0.6h at the speed of 150 rpm. Argon is introduced into the reaction kettle to ensure that the pressure in the reaction kettle reaches 1.7MPa, and the reaction kettle is continuously stirred for 3.6 hours. And after stirring, spray drying the reaction solution at 164 ℃ to obtain dry composite starch, crosslinking for 2.4 hours at 205 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. A TEM image of the activated carbon obtained by this method under normal temperature and pressure is shown in fig. 15. The degree of crosslinking and tap density of the two are shown in the attached table.
Example nine:
1kg of a mixture of corn starch and potato starch (the mass ratio of the two is 2.5. The starch slurry was heated to 52 ℃ at a heating rate of 6 ℃/min and stirred at 470rpm for 0.5h. Introducing helium into the reaction kettle to ensure that the pressure in the reaction kettle reaches 4.3MPa, and continuously stirring for 5.2h. And after stirring, spray drying the reaction solution at 170 ℃ to obtain dry composite starch, crosslinking for 5.6 hours at 170 ℃ under the protection of nitrogen, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. A TEM image of the activated carbon obtained by this method and under normal temperature and pressure is shown in fig. 17. The degree of crosslinking and tap density of the two are shown in the attached table.
Example ten:
1kg of corn starch, 0.33kg of phosphorus oxychloride and 4kg of deionized water are added into a closed reaction kettle and stirred for 1 hour at 260rpm, so that the materials are uniformly mixed. The starch slurry was warmed to 44 ℃ at a ramp rate of 10 ℃/min and stirred for 1h at 260 rpm. Introducing nitrogen into the reaction kettle to ensure that the pressure in the reaction kettle reaches 2.3MPa, and continuously stirring for 1.6h. And after stirring, spray drying the reaction solution at 160 ℃ to obtain dry composite starch, crosslinking for 7 hours at 157 ℃ under the protection of nitrogen and argon, and then carbonizing, activating and purifying to obtain the solid supercapacitor activated carbon. A TEM image of the activated carbon obtained by this method and under normal temperature and pressure is shown in fig. 19. The crosslinking degree and tap density of both are shown in the following table.
Figure DEST_PATH_IMAGE001
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and the technical solutions of the embodiment are equally replaced by one or more technical parameters to form a new technical solution, which is also within the scope of the present invention; it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A preparation method of starch with high crosslinking degree is characterized by comprising the following steps:
s1, adding starch, a cross-linking agent and deionized water into a closed reaction kettle in proportion, and stirring for 0.5-1h at the rotating speed of 40-500rpm to uniformly mix the raw materials to prepare starch slurry; wherein the mass ratio of the starch to the cross-linking agent to the deionized water is (1);
s2, heating the starch slurry prepared in the step S1 to 40-60 ℃ at a heating rate of 3-10 ℃/min, and stirring at a constant speed of 40-500rpm for 0.5-1h;
s3, filling inert gas into the reaction kettle until the pressure in the reaction kettle is 0.2-5MPa, and continuously stirring for 0.5-6h;
and S4, after stirring is finished, spray drying the reaction solution at 150-170 ℃ to obtain dry composite high-crosslinking-degree starch.
2. The method for preparing starch with high degree of crosslinking according to claim 1, wherein: in the step S1, the starch is one or more of potato starch, corn starch and wheat starch.
3. The method for preparing starch with high degree of crosslinking according to claim 1, wherein: in the step S1, the cross-linking agent is one or a combination of more of epichlorohydrin, phosphorus oxychloride, sodium trimetaphosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.
4. The method for preparing starch with high degree of crosslinking according to claim 1, wherein: in the step S3, the inert gas is one or a combination of nitrogen, argon and helium.
5. Use of a starch with a high degree of cross-linking, obtainable by the process according to claim 1, wherein: and (3) crosslinking the dry composite high-crosslinking-degree starch prepared in the step (S4) for 0.5-10h at 120-220 ℃ under the protection of inert gas, and then carbonizing, activating and purifying to prepare the super-capacitor activated carbon.
6. Use of a starch with a high degree of cross-linking according to claim 5, characterized in that: the super-capacitor activated carbon is of a solid structure, the crosslinking degree is 60-80%, and the tap density is 0.45-0.65g/ml.
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