CN105236406A - Supercapacitor spherical active carbon preparation method - Google Patents
Supercapacitor spherical active carbon preparation method Download PDFInfo
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- CN105236406A CN105236406A CN201510579942.4A CN201510579942A CN105236406A CN 105236406 A CN105236406 A CN 105236406A CN 201510579942 A CN201510579942 A CN 201510579942A CN 105236406 A CN105236406 A CN 105236406A
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- starch
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- ultracapacitor
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- inert atmosphere
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229920002472 Starch Polymers 0.000 claims abstract description 131
- 235000019698 starch Nutrition 0.000 claims abstract description 131
- 239000008107 starch Substances 0.000 claims abstract description 128
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000012298 atmosphere Substances 0.000 claims abstract description 21
- 239000004005 microsphere Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000006641 stabilisation Effects 0.000 claims abstract description 11
- 238000011105 stabilization Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 239000012190 activator Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 230000004913 activation Effects 0.000 claims description 20
- 239000002585 base Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005507 spraying Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001592 potato starch Polymers 0.000 claims description 6
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 5
- 235000013399 edible fruits Nutrition 0.000 claims description 5
- 235000021374 legumes Nutrition 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 238000001694 spray drying Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003990 capacitor Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 240000008790 Musa x paradisiaca Species 0.000 description 4
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- -1 comprises: gac Substances 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention discloses a supercapacitor spherical activated carbon preparation method, which comprises: mixing starch and a catalyst in water to prepare a starch aqueous solution, and carrying out spray-drying to obtain a dried starch mixture; carrying out heating and stabilization treatment on the dried starch mixture in an inert atmosphere to obtain starch-based carbon microspheres; and uniformly mixing the starch-based carbon microspheres and an activator, drying the water, heating under an inert atmosphere, activating, cooling, taking out, and washing the activated product to achieve a neutral state to obtain the starch-based active carbon microspheres. According to the present invention, the supercapacitor spherical activated carbon maintain the good starch sphere, and the prepared supercapacitor adopting the supercapacitor spherical activated carbon as the supercapacitor electrode has excellent electrochemical performance, and has high electrical capacitance and good cycle stability under high current conditions.
Description
Technical field
The present invention relates to a kind of preparation of starch base high-specific surface area ball shape active carbon, belong to electrode material for super capacitor technology of preparing, particularly the preparation method of this gac.
Background technology
At present, in many Application Areass, more and more higher to the power density requirements of energy storage device, beyond the ability to bear of present battery.In this context, a kind of take into account between traditional physical capacitor and secondary cell both power densities and energy density advantage novel energy-storing device---ultracapacitor is rapidly developed.Developed country is devoted to the research and development of ultracapacitor always, and some product realizes commercialization in succession.Ultracapacitor is one of very important field in electrical vehicular power exploitation in recent years.USDOE has formulated corresponding evolutionary operation(EVOP) to the exploitation of electric vehicle ultracapacitor.The researchs in ultracapacitor such as Japan NEC, Panasonic, EPCOS, Honda Company are also very active, and started actively to introduce to the market.In addition, French Saft Groupe Sa, Korea S NESE etc. are also in the Application and Development of stepping up electric vehicle ultracapacitor.China also has minority ultracapacitor enterprise to set up in the beginning of this century, and National 863 plan has been included in the applied research of research and development especially in power tool of current ultracapacitor in.Harbin Ju Rong company, Shanghai Ao Wei company etc. have also carried out series of tasks in the exploitation of electric vehicle ultracapacitor.Ultracapacitor also claims double layer capacitor, is a kind of Novel energy storage apparatus.It in seconds can complete charging usually, and having capacity large (larger than conventional capacitor electrical capacity 20 ~ 200 times), power in addition, high (specific power is greater than 5000WKg
-1), have extended cycle life (more than 10W time), use temperature wide (-40 ~ 60 DEG C), the feature such as economic environmental protection.Super capacitor can be widely used in the different application scenarios such as auxiliary peak power, standby power supply, storing, regenerating energy, substitute electric power, in fields such as Industry Control, wind light generation, the vehicles, intellectual water meter, power tool, military projects, there is boundless development prospect, particularly in certain applications scene, there is very large performance advantage.
At present, the electrode materials overwhelming majority that ultracapacitor uses is porous carbon materials, mainly comprises: gac, fiber, carbon aerogels, high-density graphite, high reactivity MCMB and carbon nanotube etc.In addition, also rare metal oxide and conductive polymers etc. is had.In all ultracapacitors using carbon material as electrode, gac is the one be employed the earliest, and the research of people to gac is simultaneously the most deep, it is produced and application is also the most extensive.The raw materials for production of gac mainly contain plant and the large class of mineral substance two.Plant mainly various trees as coconut husk, stalk etc., or wood chip, rice husk etc.Though timber is renewable resources, due to arboreal growth cycle length and the restriction by environment protection, in a large number activated carbon raw material can not be used as.
Starch is as a kind of emerging carbonaceous material precursor, not only there is the advantages such as traditional biological material low stain, recyclability, wide material sources, economic serviceability, also there is the advantage that foreign matter content is low, have natural globosity, the high uniqueness of carbon element content.In recent years, domestic rare take starch as the report that ultracapacitor gac (AC) prepared by raw material.
China Patent No. is separately had to be, 200810053417.9, disclose a kind of preparation method of starch based active carbon microballoons with high specific surface area, belong to the technology of preparing of activated carbon microballon.The method process comprises: with the fruit kind of starch of Cereal starch, potato starch, legume starch and banana and bajiao banana for raw material, raw material carries out constant temperature oxidation process in oxidizing atmosphere; By Sumstar 190 under nitrogen protection, in charring furnace, carry out charing process, the obtained starch-based carbon microsphere keeping ative starch particle shape; Obtained carbon microspheres and activator are carried out hybrid infusion, dries, by the mixture that obtains under nitrogen protection, in activation furnace, carry out activation treatment; Activation after product, through washing, centrifugation, drying, obtains starch based active carbon microballoons with high specific surface area.China Patent No. is 201110068703.4, the preparation method of disclosed ultracapacitor active carbon/carbon combined electrode, and step comprises: dried by Cereal starch and put into carbide furnace, under nitrogen protection, constant temp. heating process obtains starch base carbon; Obtained starch base carbon and ZnCl2 and FeCl3 are mixed, dry, activates in an inert atmosphere, pass into acetylene gas, obtained starch base active carbon/carbon matrix material; Mixed with PVDF by obtained starch base active carbon/carbon matrix material, add N-Methyl pyrrolidone and stir into pulp-like, be evenly coated in nickel foam, dry, compressing tablet obtains ultracapacitor active carbon/carbon compound electric pole piece.Above-mentioned patent is all that directly starch is carried out carbonizing treatment at carbide furnace obtains starch-based carbon, and the hydroxyl of the Mierocrystalline cellulose in starch etc. not easily dewaters, and be easy to left-handed conversion of glucose, the carbonation rate of starch is low.
Summary of the invention
The invention provides a kind of preparation method of ultracapacitor ball shape active carbon, its objective is the preparation method that a kind of raw material sources are extensive, cheap, production cost is low activated carbon for super capacitors is provided, it take starch as raw material, stabilized under catalyzer-charing and activation step, prepare ball shape active carbon, this gac maintains good spherical of starch, has excellent chemical property as ultracapacitor prepared after electrode of super capacitor.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for ultracapacitor ball shape active carbon, is characterized in that, the method comprises the steps:
(1) by starch and catalyzer in mass ratio 10 ~ 1:1 be blended in water, be configured to the aqueous solution that starch concentration is 5 ~ 50%, spraying dry obtains dry starch mixture; Described starch mixture comprises starch and catalyzer;
(2) by the starch mixture after spraying dry, be warming up to 150 ~ 500 DEG C under an inert atmosphere and carry out stabilization treatment 4 ~ 24 hours, obtain the starch-based carbon microsphere with elementary pore structure;
(3) starch-based carbon microsphere is mixed for 1:1 ~ 10 in mass ratio with activator, after drying moisture, intensification degree to 300 ~ 900 DEG C under an inert atmosphere, soak time is 1 ~ 8h, take out after cooling, by the washing of gained activation products to neutral, obtain starch base activated carbon microballon.
Described starch is potato starch, legume starch or fruit kind of starch.
Catalyzer in described step (1) is phosphoric acid, phosphoric acid hydrogen ammonia, primary ammonium phosphate, ammonium chloride.
Activator in described step (3) is the salt of alkali or alkaline earth metal oxide or aobvious alkalescence.Activator can be that alkali is if potassium hydroxide KOH, sodium hydroxide NaOH or alkaline earth metal oxide are as Na
2o, and the salt of all aobvious alkalescence is as sodium carbonate etc.
In the present invention, described starch is the fruit kind of starch of potato starch, legume starch and banana and bajiao banana.Potato starch can be potato, corn, wheat or tapioca (flour) etc.
In the present invention, said inert atmosphere can be nitrogen or argon gas.
Compared with prior art, the present invention has the following advantages:
(1) raw material that the present invention is used is starch, has advantage that is cheap, wide material sources, and is renewable resources.Farm crop at present for Starch Production mainly contain corn, cassava, potato, wheat etc., so starch resource is very abundant and cheap.
(2) the ultracapacitor gac that starch of the present invention is prepared after the catalyst stabilizations such as ammonium hydrogen phosphate maintains good spherical of starch, as ultracapacitor prepared after electrode of super capacitor, there is excellent chemical property, there is high-capacitance and good cyclical stability under conditions of high current.Especially the starch base activated carbon microballon prepared under alkali charcoal ratio is 4:1 condition, has good high rate performance.
It is raw material with rice bran that Chinese patent CN103936006 discloses a kind of, adopts alkalescence or acidic activated reagent to prepare the activation method of super capacitor active carbon, although the method technique is simple.But the gac obtained in the method fails to provide its parameter such as aperture, specific surface area character in detail.Can go out to find out in the gac scanning electron microscope simultaneously provided from the method, owing to there is no the preconditioning process of catalyzer in early stage, the gac that direct charing obtains has destroyed the spheroid shape form of original starch in rice bran, in high temperature carbonization process, spherical having there occurs is foamed and melts also, thus can not get the gac of the spherical morphology of high specific surface area, and gac ash to fly content higher.Chinese patent CN101950683 discloses with a kind of glucose for raw material, adopts whipping agent in autoclave after pre-treatment, then through physically activated, though also hemispheric gac can be obtained; But its complex manufacturing, production cost is high, and amplification quantity exists great potential safety hazard after producing.
(3) production technique of the present invention is simple, easy to operate, easily realizes scale operation.
Embodiment
Ultracapacitor ball shape active carbon of the present invention, it take starch as raw material, obtained through stabilization, charing and activation step after spraying dry.Concrete implementation step is as follows:
Embodiment 1
Step one: the potato starch by particle diameter being 100 microns, as yam starch mixes than for 8:1 by solid masses with primary ammonium phosphate, be dissolved in appropriate distilled water, be made into the starch solution that mass percent concentration is 10%, spraying dry, obtain dry starch mixture, this starch mixture comprises starch and catalyzer primary ammonium phosphate;
Step 2: the starch mixture that spraying dry is good is placed in tube type resistance furnace, is warming up to 150 ~ 240 DEG C and carries out stabilization treatment 4 ~ 6 hours, obtain the starch-based carbon microsphere with elementary pore structure under the inert atmosphere of nitrogen or argon gas;
Step 3: by starch-based carbon microsphere and KOH saturated solution in mass ratio (starch: KOH) mix for 1:3, oven dry moisture is placed in resistance furnace and activates, under inert atmosphere, activation temperature is 500 ~ 800 DEG C, soak time is 1 ~ 8h, take out after cooling, gained activation products use dilute hydrochloric acid and distilled water wash to neutral respectively, obtain starch base activated carbon microballon AC-1.
Described starch base activated carbon microballon AC-1 is ball shape active carbon of the present invention.
Embodiment 2
Step one: the legume starch by particle diameter being 100 microns, as pea starch mixes than for 5:1 by solid masses with phosphoric acid hydrogen ammonia, be dissolved in appropriate distilled water, be made into the starch solution that mass percent concentration is 5%, spraying dry, obtain dry starch mixture, this starch mixture comprises starch and catalyzer phosphoric acid hydrogen ammonia;
Step 2: the starch mixture that spraying dry is good is placed in tube type resistance furnace, is warming up to 200 ~ 300 DEG C under an inert atmosphere and carries out stabilization treatment 4 ~ 10 hours, obtain the starch-based carbon microsphere with elementary pore structure;
Step 3: by starch-based carbon microsphere and NaOH saturated solution in mass ratio (starch: NaOH) mix for 1:10, oven dry moisture is placed in resistance furnace and activates, under inert atmosphere, activation temperature is 500 ~ 800 DEG C, soak time is 1 ~ 8h, take out after cooling, gained activation products use dilute hydrochloric acid and distilled water wash to neutral respectively, obtain starch base activated carbon microballon AC-2.
Described starch base activated carbon microballon AC-2 is ball shape active carbon of the present invention.
Embodiment 3
Step one: the fruit kind of starch by particle diameter being 100 microns, as Semen Castaneae starch mixes than for 10:1 by solid masses with phosphoric acid, be dissolved in appropriate distilled water, be made into the starch solution that mass percent concentration is 30%, by starch solution spraying dry, obtain dry starch mixture, this starch mixture comprises Semen Castaneae starch and phosphoric acid;
Step 2: the starch mixture that spraying dry is good is placed in tube type resistance furnace, is warming up to 300 ~ 500 DEG C under an inert atmosphere and carries out stabilization treatment 4 ~ 6 hours, obtain the starch-based carbon microsphere with elementary pore structure;
Step 3: by saturated to starch-based carbon microsphere and KOH easily in mass ratio (starch: KOH) mix for 1:4, oven dry moisture is placed in resistance furnace and activates, under inert atmosphere, activation temperature is 500 ~ 900 DEG C, soak time is 1 ~ 8h, take out after cooling, gained activation products use dilute hydrochloric acid and distilled water wash to neutral respectively, obtain starch base activated carbon microballon AC-3.
Described starch base activated carbon microballon AC-3 is ball shape active carbon of the present invention.
Embodiment 4
Step one: be that 100 microns of yam starchs mix than for 4:1 by solid masses with ammonium hydrogen phosphate by particle diameter, be dissolved in appropriate distilled water, be made into the starch solution that mass percent concentration is 10%, by starch solution spraying dry, obtain dry starch mixture, this starch mixture comprises yam starch and ammonium hydrogen phosphate;
Step 2: the starch mixture that spraying dry is good is placed in tube type resistance furnace, is warming up to 160 ~ 240 DEG C under an inert atmosphere and carries out stabilization treatment 10 ~ 24 hours, obtain the starch-based carbon microsphere with elementary pore structure;
Step 3: by saturated to starch-based carbon microsphere and KOH easily in mass ratio (starch: KOH) mix for 1:4, oven dry moisture is placed in resistance furnace and activates, under inert atmosphere, activation temperature is 500 ~ 800 DEG C, soak time is 1 ~ 8h, take out after cooling, gained activation products use dilute hydrochloric acid and distilled water wash to neutral respectively, obtain starch base activated carbon microballon AC-4.
Described starch base activated carbon microballon AC-4 is ball shape active carbon of the present invention.
Embodiment 5
Step one: be that 100 microns of yam starchs mix than for 4:1 by solid masses with phosphoric acid by particle diameter, be dissolved in appropriate distilled water, be made into the starch solution that mass percent concentration is 50%, spraying dry, obtain dry starch mixture;
Step 2: the starch mixture that spraying dry is good is placed in tube type resistance furnace, is warming up to 160 ~ 240 DEG C under an inert atmosphere and carries out stabilization treatment 4 ~ 6 hours, obtain the spherical starch based carbon microsphere with elementary pore structure;
Step 3: by saturated to starch-based carbon microsphere and KOH easily in mass ratio (starch: KOH) mix for 1:4, oven dry moisture is placed in resistance furnace and activates, under inert atmosphere, activation temperature is 500 ~ 900 DEG C, soak time is 1 ~ 8h, take out after cooling, gained activation products use dilute hydrochloric acid and distilled water wash to neutral respectively, obtain starch base activated carbon microballon AC-5.
Described starch base activated carbon microballon AC-5 is ball shape active carbon of the present invention.
Embodiment 6
Step one: be that 100 microns of yam starchs mix than for 1:1 by solid masses with ammonium chloride by particle diameter, be dissolved in appropriate distilled water, be made into the starch solution that mass percent concentration is 10%, spraying dry, obtain dry starch;
Step 2: the starch that spraying dry is good is placed in tube type resistance furnace, is warming up to 150 ~ 240 DEG C under an inert atmosphere and carries out stabilization treatment 4 ~ 24 hours, obtain the starch-based carbon microsphere with elementary pore structure;
Step 3: by saturated to starch-based carbon microsphere and KOH easily in mass ratio (starch: KOH) mix for 1:4, oven dry moisture is placed in resistance furnace and activates, under inert atmosphere, activation temperature is 500 ~ 900 DEG C, soak time is 1 ~ 8h, take out after cooling, gained activation products use dilute hydrochloric acid and distilled water wash to neutral respectively, obtain starch base activated carbon microballon AC-6.
Described starch base activated carbon microballon AC-6 is ball shape active carbon of the present invention.
The ultracapacitor ball shape active carbon prepared arbitrarily by embodiment 1-6 and binding agent emulsion take according to the ratio of 8: 2, add 0.1ml deionized water to mix, mixture is evenly coated in current collector aluminum foil, dry 12h at 120 DEG C, with powder compressing machine pressurize 30s under 15Mpa, vacuum-drying, the electrode obtained sheet is assembled into the button-shaped ultracapacitor of simulation to carry out the test of chemical property, the chemical property index of each active carbon electrode material is as follows:
As can be seen from the above table, embodiment 4 best results, catalyst content is higher, and the promotion for dehydration is more obvious, starch and catalyzer higher than 1:1.
Claims (4)
1. a preparation method for ultracapacitor ball shape active carbon, is characterized in that, the method comprises the steps:
(1) by starch and catalyzer in mass ratio 10 ~ 1:1 be blended in water, be configured to the aqueous solution that starch concentration is 5 ~ 50%, spraying dry obtains dry starch mixture; Described starch mixture comprises starch and catalyzer;
(2) by the starch mixture after spraying dry, be warming up to 150 ~ 500 DEG C under an inert atmosphere and carry out stabilization treatment 4 ~ 24 hours, obtain the starch-based carbon microsphere with elementary pore structure;
(3) starch-based carbon microsphere is mixed for 1:1 ~ 10 in mass ratio with activator, after drying moisture, intensification degree to 300 ~ 900 DEG C under an inert atmosphere, soak time is 1 ~ 8h, take out after cooling, by the washing of gained activation products to neutral, obtain starch base activated carbon microballon.
2. the preparation method of a kind of ultracapacitor ball shape active carbon according to claim 1, is characterized in that: described starch is potato starch, legume starch or fruit kind of starch.
3. the preparation method of a kind of ultracapacitor ball shape active carbon according to claim 1, is characterized in that: the catalyzer in described step (1) is phosphoric acid, phosphoric acid hydrogen ammonia, primary ammonium phosphate, ammonium chloride.
4. the preparation method of a kind of ultracapacitor ball shape active carbon according to claim 1, is characterized in that: the activator in described step (3) is the salt of alkali or alkaline earth metal oxide or aobvious alkalescence.
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