CN110482545A - A kind of preparation method and its usage of high-crosslinking-degree starch - Google Patents
A kind of preparation method and its usage of high-crosslinking-degree starch Download PDFInfo
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- CN110482545A CN110482545A CN201910833492.5A CN201910833492A CN110482545A CN 110482545 A CN110482545 A CN 110482545A CN 201910833492 A CN201910833492 A CN 201910833492A CN 110482545 A CN110482545 A CN 110482545A
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- starch
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- active carbon
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- 229920002472 Starch Polymers 0.000 title claims abstract description 76
- 239000008107 starch Substances 0.000 title claims abstract description 76
- 235000019698 starch Nutrition 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 61
- 239000003990 capacitor Substances 0.000 claims abstract description 31
- 238000004132 cross linking Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000746 purification Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 9
- 229920001592 potato starch Polymers 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229920002261 Corn starch Polymers 0.000 claims description 7
- 239000008120 corn starch Substances 0.000 claims description 7
- 229940099112 cornstarch Drugs 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical group CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 230000004913 activation Effects 0.000 abstract description 15
- 239000002131 composite material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 238000003763 carbonization Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000008187 granular material Substances 0.000 description 7
- 239000003610 charcoal Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The technical issues of the present invention relates to a kind of preparation method and its usages of high-crosslinking-degree starch, belong to starch based super capacitor active carbon preparation technical field, and the solution prior art starch degree of cross linking is low, and hollow structure is easy to produce after charing.Solution is the following steps are included: starch, crosslinking agent and deionized water are uniformly mixed in enclosed stirred tank, then stirred under pressure certain time at a certain temperature, is most dried afterwards, obtains composite starch, after charing, activation, purification process, super capacitor active carbon is obtained.The present invention can eliminate the hollow structure that composite starch is formed in carbonization process, prepare fine and close spherical super capacitor active carbon, improve its tap density and compacted density, help to obtain the supercapacitor of high-energy density.
Description
Technical field
The invention belongs to starch based super capacitor active carbon preparation technical fields, and in particular to be that a kind of high-crosslinking-degree forms sediment
The preparation method and its usage of powder.
Background technique
Super capacitor active carbon is a kind of high-end active carbon, the spies such as specific surface area, high-purity, high specific capacitance with super large
Point is used for supercapacitor as crucial electrode material.Current commercialized super capacitor active carbon mainly uses coconut husk or stone
Oil coke is raw material, after the process such as being carbonized, being activated, is finally crushed to certain partial size.Usual smashed active carbon claims not
Regular shape, tap density is lower, causes the compacted density of made condenser plate relatively low.It is right with the development of Downstream Market
More stringent requirements are proposed for the energy density of supercapacitor.Currently used super capacitor active carbon performance has reached pole
Limit, can not continue to lift up.
Starch is a kind of renewable resource from a wealth of sources, by being crosslinked, charing, the techniques such as activation can be made into it is spherical super
Grade capacitor active carbon, this is highly beneficial for the compacted density for improving pole piece.However, starch granules is finer and close, conventional friendship
Connection technique can only be such that the strand on its surface reacts with crosslinking agent, and internal strand is difficult full cross-linked.After charing process,
Insufficient due to being crosslinked inside starch granules, strand decomposes seriously, to form cavity, finally obtains hollow capacitor activity
Charcoal.Cause the compacted density for being coated with pole piece still relatively low, it is difficult to improve the energy density of capacitor.In addition, in charge and discharge process, electricity
Pole liquid easily infiltrates into the cavity inside super capacitor active carbon, leads to the reduction of the electrolyte in system, influences its electrochemistry
Energy.
What Liu Enhui etc. (publication number: CN107043109 A) was announced handles starch-based bio matter charcoal low-temperature carbonization, then
Purifying removal impurity, is dried after mixing with aqueous slkali, then super capacitor is made after air calcination activation, purifying, drying
Active carbon, when final product active carbon is as capacitor electrode material, compacted density is relatively low, the energy density of capacitor also compared with
It is low.
Xun Bo etc. (publication number: 201510584928.3) by spray-dried starch, heating treatment under an inert atmosphere,
Obtain the starch-based carbon microsphere with primary pore structure；Starch-based carbon microsphere is ground, is uniformly mixed with activator, in indifferent gas
Heat up activation under atmosphere；It is passed through oxidizing gas again, heating activation takes out after cooling, obtains starch base activated carbon microballon crude product, will
Starch base activated carbon microballon crude product is washed to neutrality, and drying obtains the low spherical activated charcoal of the winged content of ash.The hollow knot of its final product
Structure is serious, and compacted density is not also high.
Starch is a kind of micron-size spherical particles with spherical structure, surface compact.In general, crosslinking agent can only form sediment
Powder particles surface is crosslinked, and is difficult to penetrate into inside particle, to form hollow structure during subsequent carbonization-activation.
Summary of the invention
In order to overcome the deficiencies in the prior art, the solution prior art starch degree of cross linking is low, is easy to produce after charing
The technical issues of hollow structure, the present invention provide a kind of preparation method and its usage of high-crosslinking-degree starch.
Design concept of the invention are as follows: starch is micro- swollen in carrying out in certain temperature range, keeping starch granules pattern
While, inside crosslinking agent impregnating by pressure to particle, make starch granules homogeneous cross-link, to improve the degree of cross linking of starch, keeps away
Exempt from the hollow structure of final product, realizes the target of super capacitor active carbon high-tap density.
The present invention is achieved by the following technical programs.
A kind of preparation method of high-crosslinking-degree starch, comprising the following steps:
S1, starch, crosslinking agent and deionized water are proportionally added into enclosed reaction kettle, are stirred under 40-500rpm revolving speed
0.5-1h mixes raw material uniformly, and starch size is made；Wherein, the mass ratio of starch, crosslinking agent and deionized water is 1:0.15
~1:1.5~4；
S2, the starch size prepared in step S1 is warming up to 40-60 DEG C with 3-10 DEG C/min heating rate, and in 40-
Constant temperature stirs 0.5-1h under 500rpm revolving speed；
S3, inert gas is filled into reaction kettle, until the pressure in reaction kettle is 0.2-5MPa, continue to stir 0.5-6h；
After S4, stirring, reaction solution is spray-dried in 150-170 DEG C, obtains the compound high-crosslinking-degree starch of dry state.
Further, in the step S1, the starch is potato starch, in cornstarch, wheaten starch
One or more combinations.
Further, in the step S1, the crosslinking agent is epoxychloropropane, phosphorous oxychloride, three metaphosphoric acids
Sodium, ammonium dihydrogen phosphate, one of dihydrogen phosphate or a variety of combinations.
Further, in the step S3, the inert gas is one of nitrogen, argon gas, helium or a variety of
Combination.
A kind of application of the preparation method of high-crosslinking-degree starch, the compound high-crosslinking-degree starch of dry state obtained is in inert gas
Through 120-220 DEG C of crosslinking 0.5-10h under protection, then through charing, activation, purification process, super capacitor active carbon is made.
Further, the super capacitor active carbon is solid construction, and degree of cross linking 60-80%, tap density is
0.45-0.65g/ml。
The invention has the following beneficial effects:
In the present invention mixed liquor 40-60 DEG C at a temperature of reaction process in, starch granules volume occur slight expansion, in high pressure
Under, crosslinking agent can be diffused to smoothly inside starch granules, make full cross-linked inside and outside starch granules, and molecule is reduced in carbonization process
Chain break forms fine and close charcoal web frame, so that the formation of hollow structure is avoided, it is final to obtain the spherical of high-tap density
Super capacitor active carbon.
Detailed description of the invention
Fig. 1 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 1.
Fig. 2 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 1.
Fig. 3 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 2.
Fig. 4 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 2.
Fig. 5 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 3.
Fig. 6 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 3.
Fig. 7 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 4.
Fig. 8 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 4.
Fig. 9 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 5.
Figure 10 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 5.
Figure 11 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 6.
Figure 12 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 6.
Figure 13 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 7.
Figure 14 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 7.
Figure 15 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 8.
Figure 16 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 8.
Figure 17 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 9.
Figure 18 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 9.
Figure 19 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from embodiment 10.
Figure 20 is the scanning electron microscope microscopic appearance figure of capacitance carbon made from the corresponding comparative example of embodiment 10.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment one:
It takes 1kg potato starch, 1kg phosphorous oxychloride and 4kg deionized water that enclosed reaction kettle is added to stir under 100rpm
0.7h mixes it uniformly.Starch size is warming up to 50 DEG C with 7 DEG C/min heating rate, continuation is stirred with the speed of 100rpm
Mix 0.7h.It is passed through nitrogen into reaction kettle, pressure in kettle is made to reach 1MPa, continues to stir 0.5h.After stirring, by reaction solution
It is spray-dried in 160 DEG C, obtains dry state composite starch, under nitrogen protection, through 200 DEG C of 0.5 h of crosslinking, then carbonized,
Activation, purification process obtain solid super capacitor active carbon.The TEM figure of the active carbon obtained under this method and normal temperature and pressure is as schemed
Shown in 1.The degree of cross linking and tap density of the two are as in the attached table.
Comparative example:
It takes 1kg potato starch, 1kg phosphorous oxychloride and 4kg deionized water to be added under enclosed reaction kettle 100rpm to stir
It is even, continue to stir 0.5h.It is after stirring, reaction solution is dry, composite starch is obtained, under nitrogen protection, is handed over through 200 DEG C
Joining the 0.5 h(degree of cross linking is 70%), then through charing, activation, purification process to obtain solid super capacitor active carbon.(following embodiment
Process route is identical)
Embodiment two:
It takes 1kg wheaten starch, 0.2kg ammonium dihydrogen phosphate and 1.6kg deionized water that enclosed reaction kettle is added to stir under 300rpm
0.5h mixes it uniformly.Starch size is warming up to 40 DEG C with 3 DEG C/min heating rate, continuation is stirred with the speed of 300rpm
Mix 0.5h.It is passed through helium into reaction kettle, pressure in kettle is made to reach 5MPa, continues to stir 4h.After stirring, by reaction solution in
170 DEG C are spray-dried, and dry state composite starch is obtained, and under nitrogen protection, through 120 DEG C of 10 h of crosslinking, then are carbonized, are lived
Change, purification process obtains solid super capacitor active carbon.The TEM figure such as Fig. 3 of the active carbon obtained under this method and normal temperature and pressure
It is shown.The degree of cross linking and tap density of the two are as in the attached table.
Embodiment three:
Take mixture (the two mass ratio is 1:1), 0.4kg dihydrogen phosphate and the 3.6kg of 1kg wheaten starch and cornstarch
Deionized water is added enclosed reaction kettle and stirs 1h under 60rpm, mixes it uniformly.By starch size with 10 DEG C/min heating speed
Rate is warming up to 60 DEG C, continues to stir 0.5h with the speed of 60rpm.It is passed through argon gas into reaction kettle, pressure in kettle is made to reach 5MPa,
Continue to stir 3h.After stirring, reaction solution is spray-dried in 150 DEG C, dry state composite starch is obtained, in nitrogen protection
Under, solid super capacitor active carbon is obtained through 150 DEG C of 5 h of crosslinking, then through charing, activation, purification process.This method and room temperature
The TEM figure of the active carbon obtained under normal pressure is as shown in Figure 5.The degree of cross linking and tap density of the two are as in the attached table.
Example IV:
Take the mixture (the two mass ratio is 2:3) of 1kg potato starch and cornstarch, 0.15kg epoxychloropropane and
1.5kg deionized water is added enclosed reaction kettle and stirs 1h under 500rpm, mixes it uniformly.By starch size with 4 DEG C/min
Heating rate is warming up to 53 DEG C, continues to stir 0.5h under 500rpm speed.It is passed through nitrogen into reaction kettle, reaches pressure in kettle
To 2MPa, continue to stir 2.5h.After stirring, reaction solution is spray-dried in 165 DEG C, obtains dry state composite starch,
Under nitrogen protection, through 180 DEG C of crosslinking 4h, then through charing, activation, purification process solid super capacitor active carbon is obtained.The party
The TEM figure of the active carbon obtained under method and normal temperature and pressure is as shown in Figure 7.The degree of cross linking and tap density of the two are as in the attached table.
Embodiment five:
Take the mixture (the two mass ratio is 1:3) of 1kg wheaten starch and potato starch, 0.33kg sodium trimetaphosphate and
1.66kg deionized water is added enclosed reaction kettle and stirs 0.8h under 40rpm, mixes it uniformly.By starch size with 10 DEG C/
Min heating rate is warming up to 45 DEG C, continues to stir 1h under 40rpm speed.It is passed through helium into reaction kettle, reaches pressure in kettle
To 0.2MPa, continue to stir 6h.After stirring, reaction solution is spray-dried in 155 DEG C, obtains dry state composite starch,
Under nitrogen protection, through 140 DEG C of 8 h of crosslinking, then through charing, activation, purification process solid super capacitor active carbon is obtained.It should
The TEM figure of the active carbon obtained under method and normal temperature and pressure is as shown in Figure 9.The degree of cross linking and tap density of the two such as subordinate list institute
Show.
Embodiment six:
Take 1kg cornstarch, 0.3kg sodium trimetaphosphate and ammonium dihydrogen phosphate mixture (the two mass ratio be 1:2) and
1.66kg deionized water is added enclosed reaction kettle and stirs 1h under 420rpm, mixes it uniformly.By starch size with 8 DEG C/min
Heating rate is warming up to 55 DEG C, continues to stir 0.6h under 420rpm speed.It is passed through nitrogen and argon gas into reaction kettle, makes in kettle
Pressure reaches 1.5MPa, continues to stir 3.5h.After stirring, reaction solution is spray-dried in 167 DEG C, it is multiple to obtain dry state
Starch is closed, under nitrogen and helium protection, obtains solid surpass through 175 DEG C of 4.5 h of crosslinking, then through charing, activation, purification process
Grade capacitor active carbon.The TEM figure of the active carbon obtained under this method and normal temperature and pressure is as shown in figure 11.The degree of cross linking and vibration of the two
Real density is as in the attached table.
Embodiment seven:
Take the mixture of 1kg potato starch, 0.23kg dihydrogen phosphate and phosphorous oxychloride (the two mass ratio is 1:1.5)
Enclosed reaction kettle is added with 1.67kg deionized water and stirs 0.9h under 350rpm, mixes it uniformly.By starch size with 9
DEG C/min heating rate is warming up to 48 DEG C, continue to stir 0.7h under 350rpm speed.It is passed through nitrogen into reaction kettle, makes in kettle
Pressure reaches 3.5MPa, continues to stir 2.7h.After stirring, reaction solution is spray-dried in 152 DEG C, it is multiple to obtain dry state
It closes starch and obtains solid super capacitor through 135 DEG C of 7.5 h of crosslinking, then through charing, activation, purification process under nitrogen protection
Active carbon.The TEM figure of the active carbon obtained under this method and normal temperature and pressure is as shown in figure 13.The degree of cross linking and tap density of the two
As in the attached table.
Embodiment eight:
Take the mixture (the two mass ratio is 1:1.5) of 1kg wheaten starch and potato starch, 0.5kg phosphorous oxychloride and
3kg deionized water is added enclosed reaction kettle and stirs 0.6h under 150rpm, mixes it uniformly.By starch size with 4 DEG C/min
Heating rate is warming up to 58 DEG C, continues to stir 0.6h under 150rpm speed.It is passed through argon gas into reaction kettle, reaches pressure in kettle
To 1.7MPa, continue to stir 3.6h.After stirring, reaction solution is spray-dried in 164 DEG C, obtains the compound shallow lake of dry state
Powder obtains solid super capacitor activity through 205 DEG C of crosslinking 2.4h, then through charing, activation, purification process under nitrogen protection
Charcoal.The TEM figure of the active carbon obtained under this method and normal temperature and pressure is as shown in figure 15.The degree of cross linking and tap density of the two are for example attached
Shown in table.
Embodiment nine:
Take mixture (the two mass ratio is 2.5:1), the 0.8kg ammonium dihydrogen phosphate and three of 1kg cornstarch and potato starch
The mixture (the two mass ratio is 1:2.5) and 1.5kg deionized water of phosphorus oxychloride are added enclosed reaction kettle and stir under 470rpm
0.5h is mixed, mixes it uniformly.Starch size is warming up to 52 DEG C with 6 DEG C/min heating rate, is continued under 470rpm speed
Stir 0.5h.It is passed through helium into reaction kettle, pressure in kettle is made to reach 4.3MPa, continues to stir 5.2h.It, will be anti-after stirring
It answers liquid to be spray-dried in 170 DEG C, obtains dry state composite starch, under nitrogen protection, through 170 DEG C of 5.6 h of crosslinking, then pass through
Charing, activation, purification process obtain solid super capacitor active carbon.The TEM of the active carbon obtained under this method and normal temperature and pressure
Figure is as shown in figure 17.The degree of cross linking and tap density of the two are as in the attached table.
Embodiment ten:
It takes 1kg cornstarch, 0.33kg phosphorous oxychloride and 4kg deionized water that enclosed reaction kettle is added to stir under 260rpm
1h mixes it uniformly.Starch size is warming up to 44 DEG C with 10 DEG C/min heating rate, continues to stir with the speed of 260rpm
1h.It is passed through nitrogen into reaction kettle, pressure in kettle is made to reach 2.3MPa, continues to stir 1.6h.After stirring, by reaction solution in
160 DEG C are spray-dried, and dry state composite starch is obtained, under nitrogen and argon gas protection, through 157 DEG C of crosslinking 7h, then through charcoal
Change, activate, purification process obtains solid super capacitor active carbon.The TEM of the active carbon obtained under this method and normal temperature and pressure schemes
As shown in figure 19.The degree of cross linking of the two and tap density are as shown in the table.
The above description is only a preferred embodiment of the present invention and is not intended to restrict the invention, in embodiment technical solution
Same replacement is carried out to single or multiple technical parameters and forms new technical solution, equally all in claimed model
In enclosing；For those skilled in the art, the present invention can carry out various modifications and variations.It is all in spirit of the invention and
Any modification, equivalent replacement, improvement and so within principle, should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of preparation method of high-crosslinking-degree starch, it is characterised in that the following steps are included:
S1, starch, crosslinking agent and deionized water are proportionally added into enclosed reaction kettle, are stirred under 40-500rpm revolving speed
0.5-1h mixes raw material uniformly, and starch size is made；Wherein, the mass ratio of starch, crosslinking agent and deionized water is 1:0.15
~1:1.5~4；
S2, the starch size prepared in step S1 is warming up to 40-60 DEG C with 3-10 DEG C/min heating rate, and in 40-
Constant temperature stirs 0.5-1h under 500rpm revolving speed；
S3, inert gas is filled into reaction kettle, until the pressure in reaction kettle is 0.2-5MPa, continue to stir 0.5-6h；
After S4, stirring, reaction solution is spray-dried in 150-170 DEG C, obtains the compound high-crosslinking-degree starch of dry state.
2. a kind of preparation method of high-crosslinking-degree starch according to claim 1, it is characterised in that: in the step S1
In, the starch is one of potato starch, cornstarch, wheaten starch or a variety of combinations.
3. a kind of preparation method of high-crosslinking-degree starch according to claim 1, it is characterised in that: in the step S1
In, the crosslinking agent is epoxychloropropane, phosphorous oxychloride, sodium trimetaphosphate, ammonium dihydrogen phosphate, one in dihydrogen phosphate
Kind or a variety of combinations.
4. a kind of preparation method of high-crosslinking-degree starch according to claim 1, it is characterised in that: in the step S3
In, the inert gas is one of nitrogen, argon gas, helium or a variety of combinations.
5. a kind of application of the preparation method of high-crosslinking-degree starch as described in claim 1, it is characterised in that: the step S4
The compound high-crosslinking-degree starch of dry state obtained is under inert gas protection through 120-220 DEG C of crosslinking 0.5-10h, then is carbonized, lived
Change, purification process, super capacitor active carbon is made.
6. a kind of application of the preparation method of high-crosslinking-degree starch according to claim 5, it is characterised in that: described is super
Grade capacitor active carbon is solid construction, degree of cross linking 60-80%, tap density 0.45-0.65g/ml.
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