CN103539118B - A kind of method for preparation of active carbon for ultracapacitor - Google Patents
A kind of method for preparation of active carbon for ultracapacitor Download PDFInfo
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- CN103539118B CN103539118B CN201310521509.6A CN201310521509A CN103539118B CN 103539118 B CN103539118 B CN 103539118B CN 201310521509 A CN201310521509 A CN 201310521509A CN 103539118 B CN103539118 B CN 103539118B
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a kind of method for preparation of active carbon for ultracapacitor, comprise the pre-treatment of rice husk raw material, charing, pre-treatment, activation, aftertreatment, pre-treatment comprises alkaline reagents pre-treatment, mix reagent pre-treatment and water infiltration pre-treatment.Rice husk raw material sources used are extensive, are conducive to reducing costs.Gac prepared by the method has potential application prospect on ultracapacitor.
Description
Technical field
The present invention relates to a kind of method for preparation of active carbon for ultracapacitor, belong to technical field of new energies.
Background technology
China has become sale of automobile market the biggest in the world, and the sustainable growth of consumption of petroleum and the continuous increase of pollutant emission, become automobile industry development problem demanding prompt solution.Energy-conservation and the new-energy automobile such as hybrid electric vehicle, pure electric automobile, fuel-cell vehicle becomes reasonable evolutionary path.Some large motor corporations have all carried out the research and development of correlation technique both at home and abroad, and part realizes commercialization.
Ultracapacitor is a kind of very promising power cell, has specific power high, has extended cycle life, high current charge-discharge, environmental friendliness, safety and non-maintaining advantage.Its critical material is gac, directly has influence on the performance of ultracapacitor.At present, the raw materials of conventional gac mainly contains the mixing raw material etc. of petroleum-based feedstock, coal-based feedstocks, mud, plant material and their compositions.
Petroleum-based feedstock mainly contains pitch, refinery coke and organic compound, such as, the Chinese patent of application publication number CN102491320A discloses a kind of pitch-based active carbon with superhigh specific surface area and preparation method thereof, application publication number CN102176384A take needle coke as the preparation method that graphite microcrystal carbon prepared by raw material, the Chinese patent of publication number CN1693189A discloses a kind of preparation method taking refinery coke as raw material preparation and be rich in mesopore active carbon with high specific surface area, the Chinese patent of publication number CN101269811A discloses the method that non-fusible pitch prepares high-carbon yield ball shape active carbon, publication number is that the Chinese patent of CN1334237A discloses and a kind ofly makes by the partly isotropic pitch of oxidation particle shape the Large Copacity absorbent charcoal material that can be used for double layer capacitor.
Coal, has also been used to prepare activated carbon raw material.The Chinese patent of application publication number CN102583373A discloses the method preparing gac with coal, the Chinese patent of application publication number CN102674344A discloses the method for producing gac with coal tar, the Chinese patent of application publication number CN102153081A discloses a kind of method utilizing coal directly-liquefied residue to prepare gac, the Chinese patent of application publication number CN101717085A discloses method activated carbon microballon being prepared by the mixture of coal-tar pitch and additive, the Chinese patent of publication number CN101654246A discloses coal dust, potassium permanganate and coal tar are squeezed into the method that particle prepares active carbon similar to molecular sieve, the Chinese patent of application publication number CN101774578A discloses the method utilizing coal plasma pyrolysis to produce gac.But it is high to there is ash content in coal activated carbon, the shortcomings such as impurity is many.
Also research is had to prepare gac using mud as raw material, the Chinese patent of application publication number CN102530941A discloses the preparation method of sludge-based activated carbon, the Chinese patent of application publication number CN102757047A discloses a kind of preparation method of column sludge-based activated carbon, the Chinese patent of application publication number CN102658084A discloses a kind of preparation method of nickelous nitrate modified sewage sludge absorbent charcoal, the Chinese patent of application publication number CN102689898A discloses the method for the method of active sludge continuous seepage gac, the Chinese patent of application publication number CN102701200A discloses the method that gac is prepared in the pyrolysis of a kind of municipal sludge two step.
Several raw material may be mixed together prepares gac, the Chinese patent of application publication number CN101734656A discloses a kind of method being prepared active carbon with high specific surface area by coal and waste or used plastics microwave, the Chinese patent of publication number CN101092239A discloses a kind of coal doping pecan shell base and prepares active carbon method, the Chinese patent of application publication number CN102381705A discloses the method that a kind of microwave thermal activated coal coke tar refuse/sludge fermentation body produces gac, the Chinese patent of application publication number CN101767785A discloses the method that excess sludge and corn cob are mixed with peracidity group content gac, the Chinese patent of publication number CN1868874A discloses and adopts coal and straw or like vegetable to starch the method preparing gac.
Plant material is because of its wide material sources, cheap, is subject to extensive concern.Patent No. US005883040A U.S. patents discloses a kind of method utilizing agricultural waste material to prepare gac, and agricultural waste material adds heat abstraction organic volatile at 250 ~ 550 DEG C, and 600 ~ 800 DEG C of charings further, activation obtain gac.Patent No. US006537947B1 U.S. patents discloses a kind of low density agricultural wastes at atmosphere of inert gases 700 ~ 750 DEG C charing 1 ~ 2h, utilize carbonic acid gas or water vapour at 800 ~ 950 DEG C of activation 3 ~ 12h, then at 260 ~ 400 DEG C of oxidation 3 ~ 6h, gac is obtained.Patent No. US8318356B2 U.S. patents disclose a kind of with whole meal flour, Semen Maydis powder etc. for the method for activated carbon for super capacitors prepared by raw material.Whole meal flour, at nitrogen atmosphere 800 DEG C heating charing 2h, mixes with the potassium hydroxide of 46% according to the alkali charcoal ratio of 5:1, nitrogen atmosphere 800 DEG C activation 2h, then respectively with water and hydrochloric acid soln washing, dry, obtains absorbent charcoal material.The Chinese patent of publication number CN1927710A discloses a kind of method that maize straw prepares gac, the maize straw pulverized is adopted to the composite activating agent of phosphoric acid, sulfuric acid and sodium-chlor composition, under ultrasonication, immersion, microwave activation, supersound washing obtains gac.It is raw material with agricultural crop straw that the Chinese patent of publication number CN101037200A discloses a kind of, successively through the processing step of drying and crushing, charing, activation, obtains organic system activated carbon for super capacitors material.It is raw material with bamboo that the Chinese patent of publication number CN101117219A discloses a kind of, through 400 ~ 550 DEG C of charing process 1 ~ 2 hour, carbonized material is mixed by 1:1.0 ~ 2.0:0.5 ~ 1.3 weight proportion with sodium hydroxide and potassium hydroxide, in 700 ~ 800 DEG C of activation treatment 2 ~ 3 hours, washing acid neutralization, dry and obtain gac.
The patent No. be US5064805 U.S. patents disclose a kind of method preparing bigger serface, low sulphur content gac.As the coconut husk charcoal of carbonaceous material, the potassium hydroxide with moisture 2 ~ 25%, mixes according to mass ratio 1:2 ~ 1:6.When water-content is less than 2%, require higher activator melt temperature, high to equipment requirements, water-content higher than 25% time, activate insufficient.Can not activate completely when activator is less, and time too high, the pore structure of gac is caved in, preferred 1:3 ~ 1:5 heat-activated.The Chinese patent of publication number CN1919730A discloses a kind of method of preparing low ash high specific surface area active carbon from coconut shell slag, and coconut-shell slag is deliming after hot wash, the further deliming of acid treatment obtains de-ashed coconut shell residue under normal temperature; De-ashed coconut shell residue obtains active carbon with high specific surface area through charing, activation, washing, oven dry.The Chinese patent of publication number CN1824604A discloses one with waste hard shell for raw material, through screening, fragmentation, 400 ~ 500 DEG C carbonize process 1 ~ 2 hour, carbonized material is mixed by 1:1.0 ~ 2.5:0.4 ~ 1.2 weight proportion with sodium hydroxide and potassium hydroxide, in 700 ~ 800 DEG C of activation treatment 2 ~ 3h, be washed to pH value 6 ~ 7, after oven dry, can gac be obtained.The hard fruit shell raw material that the Chinese patent of publication number CN101177266A discloses through screening is placed in ZnCl
2in solution, ZnCl
2be 0.2:1 ~ 3:1 with the mass ratio of hard fruit shell raw material, fully stir, dry at 110 ~ 120 DEG C of temperature, the mixture after drying is carried out activation and obtains gac.The Chinese patent of publication number CN101423210A discloses the manufacture method that a kind of biological material is the active carbon for polar electric pole of raw material, biomass material is carbonized, after being mixed in proportion with alkali, under 500 ~ 600 DEG C of conditions stirred, carry out the 1st stage activation, then carry out the 2nd stage activation at 700 ~ 900 DEG C.The Chinese patent of application publication number CN102275915A discloses a kind of by fruit shell carbon material load SiO
2as activator, through aging, cleaning, dry and activation, last alkali or hydrofluoric acid or fluorochemical remove SiO
2, then prepare after steam activation there is balanced mesoporous and micropore ratio gac.The Chinese patent of application publication number CN102627276A disclose fill dry shell ceramic pyrolysis reactor in be full of air, completely airtight, then under the pyrolysis temperature of 700 ~ 1000 DEG C, pyrolysis 1 ~ 10h obtains gac.The Chinese patent of application publication number CN102730683A discloses the method that electrode material for super capacitor prepared by a kind of use cotton stalk matrix activated carbon material; cotton stalk floods with activator mix, dries after peeling is pulverized; then under protection of inert gas or vacuum condition; temperature 500 ~ 900 DEG C is risen to the temperature rise rate of temperature 2-5 DEG C/min; constant temperature 2 ~ 5h activates, and obtains absorbent charcoal material.
Rice husk is a meter waste for industry processing, accounts for 20% of paddy weight.Rice husk rich cellulose, xylogen, many carboxylics pentose and ash grade, and carbon content is high, have Development volue widely as absorbent charcoal material raw material.A kind of alkali activation rice hull ash that U.S. patents discloses of patent No. US006114280A prepares the method for gac.The carbide removing silicon cleans with the hot water of 140 ~ 160 ℉, 1 part of carbide, 3 parts of hot water.Then wash with the acid of corresponding 2.5 parts of 1 part of carbide, acid concentration is 2 ~ 7%.The Chinese patent of publication number CN1039000A disclose a kind of with rice hull ash be raw material more than 128 DEG C, pressure is 2.5 kgfs/cm
2under above condition, carry out reacting the method producing gac with alkaline solution.The Chinese patent of publication number CN1203887A discloses rice hull carbon compound and mixes according to mass ratio 1:2 ~ 5 with alkali activator, and wherein alkaline matter used is KOH, NaOH, K
2cO
3, Na
2cO
3, take KOH as the best.After 300 ~ 500 DEG C of pre-treatment 20 ~ 60min, 700 ~ 850 DEG C of activation 30 ~ 120min, cooling, grinding, be soaked in water, and be washed to neutrality, it is 2500 ~ 3500 that drying obtains specific surface area
2the gac of/g.The Chinese patent of publication number CN1319033A discloses the digestion of rice hull ash causticization, and the hot water cleaning of about 140 ~ 160 ℉ leaches activated carbon granule, then uses the aqueous cleaning of 2 ~ 7% phosphoric acid, sulfuric acid or hydrochloric acid, washing, dry, obtains activated carbon granule.It is raw material that the Chinese patent of publication number CN101177264A discloses with rice hull ash, take sodium hydroxide solution as solvent reaction, is separated solid-liquid mixture, the pickling of insolubles filter cake, washing, and dehydration, drying, obtain active carbon finished products.The Chinese patent of publication number CN101264885A discloses to be produced the filter residue after water glass by rice hull ash and repeatedly washs through alkali lye, acid solution, hot water, dry, obtains gac.The NaOH solution of boiling that the Chinese patent of publication number CN101456555A discloses rice husk and 2mol/L reacts 3 ~ 6h, filter, a certain amount of distillation poach boiled of filter residue is washed, then embathes 2h with the hydrochloric acid of 1.5%, filter residue to pH value after washing acidleach is 5.5 ~ 7.0, dry; Solution KOH being mixed with 20 ~ 40% joins in dried gac, and first by moisture evaporation, in retort furnace, temperature is about 600 ~ 650 DEG C of activation 20 ~ 40min, and washing, dry, pulverize, obtain gac.The Chinese patent of application publication number CN101691225A discloses and in rice hull ash, adds alkali lye according to mass ratio 2:10 ~ 4:10, and temperature is 120 ~ 160 DEG C, reaction 5 ~ 7h.Filter, add dilute hydrochloric acid solution concussion in filter residue, suction filtration, is then washed to neutrality; Every gram of charcoal filter residue KOH solution that 18 ~ 22ml mass concentration is 23 ~ 27% floods 12 hours, and 120 ~ 140 DEG C are dried to half-dried, 600 ~ 750 DEG C of activation 18 ~ 30min, the salt acid soak of 5 ~ 10ml mass concentration 15% of every gram of filter residue after activation, washing, dries, obtains gac.The Chinese patent of application publication number CN101700883A discloses rice husk and is sieved in stove with the speed of 1000 ~ 2000kg/h from process furnace top, stove set temperature is 700 ~ 900 DEG C, rice husk under sieve carbonization-activation in stove forms charcoal shell deposition, in the sodium hydroxide solution (mass concentration is 5 ~ 10%) that charcoal shell joins its quality 2 ~ 3 times or phosphoric acid solution (mass concentration is 30 ~ 50%), 100 ~ 150 DEG C of stirring heating 2 ~ 5h, filter, breeze is washed, dry, dilute phosphoric acid solution washs, washing, dry, obtain rice hull active carbon.The Chinese patent of application publication number CN102247802A discloses rice husk at N
2in atmosphere, carbonize in 400 ~ 700 DEG C, generate charring rice husk, by alkali charcoal mass ratio 1:4 Homogeneous phase mixing solid NaOH and charring rice husk, at N
2under protection, 390 ~ 410 DEG C of preheating 25 ~ 35min, 600 ~ 900 DEG C of activation 1 ~ 2h, carry out pickling with the HCl of 0.05 ~ 0.15mo1/L, dip treating 25 ~ 35min, deionized water wash, filter, dry, obtain powder activated Carbon Materials.The Chinese patent of application publication number CN101891189A discloses rice husk 550 ~ 580 DEG C of rice hull carbon compounds of smouldering to obtain, join concentration be 20 ~ 30% sodium hydroxide solution or concentration be in the phosphoric acid solution of 20 ~ 25%, the weight of sodium hydroxide solution or phosphoric acid solution is 2 ~ 2.5 of described rice hull carbon weight, 130 ~ 140 DEG C of reaction 4 ~ 5h, filter, filter residue sealing 680 ~ 720 DEG C of activation 20 ~ 30min; Charcoal material is come out of the stove, clear water pumps into reactor after soaking, the silica 1 10 ~ 120 DEG C utilizing the first step to remain in sodium hydroxide in filter residue or phosphoric acid and first shelves gac reacts 2 ~ 3h, solid-liquid separation, filter residue is washed, dry, with concentration be 8 ~ 10% sodium hydroxide solution or concentration be 5 ~ 7% phosphate aqueous solution it is moistening, sealing, 800 ~ 840 DEG C activation 20 ~ 30min; In stove, charcoal material is come out of the stove, is immersed in water and pumps into reactor, 120 ~ 140 DEG C of reaction 3 ~ 4h, solid-liquid separation, and filter residue is washed, dry, sealing, 910 ~ 950 DEG C of activation 20 ~ 30min; In stove, charcoal material is come out of the stove, is immersed in concentration is in the phosphate aqueous solution of 3 ~ 5%, and pump into reactor 105 ~ 110 DEG C reaction 2 ~ 3h, solid-liquid separation, filter residue is washed, dry, obtains gac.The Chinese patent of application publication number CN101920966A discloses rice hull ash and soaks 1 ~ 24h at the inorganic acid solution that pH value is 0 ~ 5, inorganic acid solution and rice hull ash volume ratio are 1:0.6 ~ 5, filtration after immersion completes, after filter residue mixes according to the ratio uniform that mass ratio is 1:2 ~ 3 with one or several the mixture in sodium carbonate, sodium hydroxide, salt of wormwood, potassium hydroxide, 1 ~ 3h is activated at 600 ~ 800 DEG C, add water boil 10 ~ 40min that volume is activation products 1.5 ~ 3 times, filter, residue washing is to neutral, dry, obtain gac.It is that 1:5.2 ~ 6.8 take rice husk that the Chinese patent of application publication number CN101993070A discloses according to weight ratio, join that concentration is 53 ~ 55 degree Beaume, pH value is in the liquor zinci chloridi of 3 ~ 3.4, mixing 5 ~ 25min, high-temperature flue gas is adopted to make thermophore, be counter current contact with rice husk, direct heat transfer, 300 DEG C of charings, 630 DEG C of activation; Activated material puts into recycling bin, and be the zinc chloride dilute solution of 26 ~ 29 degree Beaume by concentration, concentration is HCl treatment, the hot wash of 33%; Breeze puts into reactor, and the sodium hydroxide mass ratio 2:3 being 30 ~ 35% by breeze and concentration adds sodium hydroxide solution, and to carry out alkali molten, and sodium hydroxide is 50 ~ 60 parts, and alkali solubility temperature is 85 ~ 100 DEG C, at this temperature insulated and stirred 2 ~ 3h; Filter, filter cake is washed, and concentration is that 33% hydrochloric acid boils and washes, and drying obtains gac.The Chinese patent of application publication number CN102001656A discloses rice husk through acid-alkali treatment again through being washed to neutral filter residue, by this filter residue and drying, with mass concentration be 20 ~ 60% zinc chloride and 2 ~ 10% Repone K altogether solution soak at 70 ~ 80 DEG C and be not less than 9h; Being taken out by filter residue pours in porcelain crucible, puts retort furnace into and activate 1 ~ 2h at 400 ~ 800 DEG C; Through mass concentration 8 ~ 12% salt acid elution, filter, be washed to neutrality, dry, obtain gac.It is raw material that the Chinese patent of application publication number CN102020272A discloses with rice hull ash, sodium hydroxide (mass concentration is 8 ~ 14% solution) and rice hull ash are 1:4.5 in mass ratio, reaction forms solidliquid mixture, filtering separation, be the ratio of 5 ~ 7:1 in the volume ratio of sulphuric acid soln and insolubles, add mass concentration be 22 ~ 30% sulphuric acid soln carry out wet distillation acid treatment activation, then use hot wash, again through washing filtering separation, drying, obtain active carbon finished products.The Chinese patent of application publication number CN102071267A discloses rice husk and water heated and boiled 50 ~ 90min, cold filtration obtains filter residue, filter residue puts into heating container, add the water of 3 ~ 4 times, start after under agitation adding sulfuric acid to be heated to boiling, after stirring and refluxing 200 ~ 240min, cold filtration, filter residue is washed with water to neutrality, put into retort furnace and be heated to 380 ~ 420 DEG C of carbonizations, the product obtained puts into heating container, add sodium hydroxide and the potassium hydroxide solution of concentration 2 ~ 4mol/L, be heated to 120 DEG C of reactions, backflow 60 ~ 240min, cold filtration, solid product puts into heating container, add liquor zinci chloridi, after being heated to 70 ~ 90 DEG C of maintenance immersion 700 ~ 750min, pour crucible into, remain with certain liquor zinci chloridi, put into retort furnace, be heated to 400 ~ 800 DEG C of activation 60 ~ 120min, salt acid elution, be washed to neutrality, dry, obtain activated carbon product.The Chinese patent of application publication number CN102515156A discloses sends rice husk spiral shell chapelet into drying tower, and the hot gas being 200 ~ 300 DEG C with temperature carries out mass heat transfer, and rice husk dehydration is less than 10%, by induced draft fan by moisture discharge chamber to moisture; Rice husk after the drying and preheating obtained is sent into reciprocating pyrolysis oven through chapelet, and 500 DEG C of pyrolysis, the gas of generation is drawn rapidly and is entered 2 grades of spray columns, and bio-oil is prepared in condensation, and the solid of generation enters the automatic collection box of solid, obtains C and SiO
2mass ratio is the pyrolysis ash of 52:48; Pyrolysis ash, after sour neutralizing treatment, is put in reactor with the aqueous sodium hydroxide solution of 0.3 ~ 0.7mol/L in the ratio of solid-to-liquid ratio 1:5 ~ 10, is warming up to 90 ~ 180 DEG C, sealing hydrolysis 1 ~ 3.5h, filter, solid-liquid separation, filter residue is activated carbon product through washing, drying.The Chinese patent of application publication number CN102786052A discloses rice husk and mixes by the impregnating ratio of 1:1.0 ~ 1:3.0 with the liquor zinci chloridi of concentration 40 ~ 60wt%, be placed in crucible soak at room temperature 16h with cover, 450 ~ 650 DEG C are warming up in retort furnace, activation 45 ~ 90min, cooling, be washed to neutrality, dry, prepare gac.The Chinese patent of publication number CN101486460A discloses rice hull ash and reacts with 8 ~ 15% aqueous sodium carbonates (in mass ratio 1:30 ~ 40) under temperature-pressure condition, reactor pressure 3 ~ 5Mpa, temperature 130 ~ 160 DEG C, reaction times 2 ~ 3h, through solid-liquid separation, gained filter residue activates 5h, pickling, washing, drying through washing, leaching concentration 10% iron(ic) chloride or ferrous sulfate, pulverize, makes active carbon finished products.The Chinese patent of publication number CN1090306A discloses temperature to be the rice husk that carbonizes under the condition of 600 ~ 650 DEG C and degree Beaume be 8 ~ 11 sodium carbonate solution by weight percentage 1:37 drop in retort, tank internal pressure is 2 ~ 3MPa, temperature is 120 ~ 130 DEG C, reaction times is 3 ~ 3.5h, solid-liquid separation, slag charcoal and 25% hydrochloric acid soln by weight percentage 5:1 carry out pickling, remove impurity, impurity is removed in reusable heat water washing, dehydration, drying are carry out 15 ~ 18min activation under the condition of 650 DEG C to produce gac in furnace temperature.The Chinese patent of application publication number CN101804988A discloses rice hull ash, solid sodium carbonate or salt of wormwood Homogeneous phase mixing by a certain percentage, be placed in High Temperature Furnaces Heating Apparatus and be warming up to 850 ~ 950 DEG C, constant temperature frit reaction 0.5 ~ 2h, be transferred in dissolution kettle and be heated to boiling dissolving 0.5 ~ 2h, filter, filter residue is washed through diluted acid, wash with water again to neutrality, filter, dry, obtain activated carbon product.As mentioned above, the gac that prepared by chemical method is suitable for ultracapacitor.Existing be gac prepared by raw material with rice husk, if the impurity such as silicon, magnesium is purified clean, the performance of ultracapacitor can be affected; Activator is uneven in carbon raw material surface arrangement, and activation can fall flat.
Summary of the invention
The object of the present invention is to provide a kind of method for preparation of active carbon for ultracapacitor, gac preparation generally has pre-treatment, charing, activation and last handling process, pre-treatment mainly carries out removal impurity to raw material, pulverizing process of Denging; The process of charing to be converting feedstock be charcoal, mainly carries out in Reaktionsofen; Activation generally has Physical, chemical method and Physical and chemical method to combine, the gac prepared by the Physical such as water vapour, carbonic acid gas is mostly microvoid structure, and chemical rule adopts the chemical reagent such as phosphoric acid, sodium hydroxide, potassium hydroxide, zinc chloride, Repone K to mix with carbon raw material as activator, complete in Reaktionsofen, obtained gac is based on mesopore.Gac general requirement specific surface area for ultracapacitor is large, mesopore accounting is high, and stable homogeneous is good, compacted density is large, electrolytic solution wetting property is good, be easy to processing.
Technical scheme of the present invention is achieved in that a kind of method for preparation of active carbon for ultracapacitor, first carries out the washing of rice husk raw material, removes impurity and moisture, the pre-treatments such as pulverizing; Under protection of inert gas, 380 ~ 450 DEG C of heating charing 1 ~ 3h, obtain carbon precursor; It is characterized in that: pre-treatment comprises alkaline reagents, mix reagent process and water infiltration: its concrete steps are as follows: 1) rice husk raw material reflux 2 ~ 24h in alkaline reagents, washing, dry, obtain alkaline reagents pre-treatment charcoal; 2) alkaline reagents pre-treatment charcoal soaks 2 ~ 24h in mix reagent, then uses the deionized water dilution of 1 ~ 3 times of volume of carbon precursor and mix reagent, stirs 1 ~ 5h, then with deionized water wash to neutral, drying, obtains mix reagent pre-treatment charcoal; 3) mix reagent pre-treatment charcoal and water are stirred to water complete wetting, add activator Keep agitation 1 ~ 3h, obtain pre-treatment charcoal; Pre-treatment charcoal heat-activated, obtains the Carbon Materials activated; The Carbon Materials of activation obtains absorbent charcoal material through last handling processes such as washing, dryings.
Maximum feature of the present invention is pre-treatment, carbon precursor is through alkalescence, mix reagent and water infiltration pre-treatment, the hole surface that alkaline reagents removal impurity stays is through mix reagent process, can form the hydrophilic radicals (can find out in infrared analysis figure) such as such as hydroxyl, carboxyl, epoxy group(ing), water infiltration is conducive to the abundant infiltration of activator at carbon surface.
Described alkaline reagents be potassium hydroxide, sodium hydroxide or their combination the aqueous solution, alkali charcoal mass ratio is 1:1 ~ 3:1; Mix reagent comprises sulfuric acid, persulphate, Vanadium Pentoxide in FLAKES, and every gram of charcoal sulfuric acid used (concentration >=95%) is 10 ~ 30ml, Vanadium Pentoxide in FLAKES 1 ~ 10g used, persulphate 1 ~ 5g used, and infiltration water is 0.8 ~ 1.5 times of carbon precursor quality.
Described activator is the one or more combination in conventional potassium hydroxide, sodium hydroxide, lithium hydroxide, zinc chloride, Repone K, phosphoric acid, salt of wormwood, preferred potassium hydroxide, sodium hydroxide or their combinations, alkali charcoal mass ratio 1:1 ~ 4:1, activation temperature 700 ~ 900 DEG C.
Positively effect of the present invention: take rice husk as raw material, wide material sources and cost is low; The method adopts rice husk raw material to carbonize into carbon precursor, by alkalescence, mix reagent and water infiltration pre-treatment carbon precursor, remove foreign ion, form the hydrophilic radicals such as hydroxyl, carboxyl and epoxy group(ing) at carbon surface, water infiltration is conducive to the abundant infiltration of activator at carbon surface, improves activation effect.Gac prepared by the method has potential application prospect on ultracapacitor.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of the gac in the embodiment of the present invention 1.
Fig. 2 is the TGA curve of the rice husk raw material in the embodiment of the present invention 1.
Fig. 3 is the infrared spectrum of alkalescence in the embodiment of the present invention 1 and mix reagent process charcoal.
Fig. 4 is the SEM photo of the gac after the activation in the embodiment of the present invention 1.
Fig. 5 is the XRD spectra of the gac after the activation in the embodiment of the present invention 1.
Fig. 6 is the absorbent charcoal material specific surface area analysis curve in the embodiment of the present invention 1.
Fig. 7 is the charging and discharging curve of the absorbent charcoal material in the embodiment of the present invention 1 for aqueous super capacitor.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described, and the specific descriptions of described embodiment just to claim of the present invention, claim includes but not limited to described embodiment content.
Embodiment 1
(1) rice husk deionized water repeatedly washs, and removes the impurity such as silt, dehydration, and temperature 80 DEG C is dried to constant weight, pulverizes.
(2) a certain amount of rice husk puts into ceramic crucible, is then placed in Reaktionsofen, connects device for recovering tail gas; Venting air, continues to pass into argon gas, is warming up to 400 DEG C with 20 DEG C/min, and constant temperature 1h, is down to room temperature, takes out carbon precursor.
(3) according to alkali charcoal mass ratio 3:1 by carbon precursor reflux 3h in potassium hydroxide aqueous solution, deionized water dilute, dehydrate, obtain alkaline purification charcoal.
(4) 5g Potassium Persulphate is taken and 5g Vanadium Pentoxide in FLAKES joins in the 25ml vitriol oil, stir, slowly be warming up to 80 DEG C, add oxygenation pretreatment charcoal 3g, constant temperature 3h, dilute with the deionized water of mixing solutions 1 times of volume, stir 1h, then use a large amount of deionized water wash, dehydration, temperature 50 C is dried to constant weight, obtains mix reagent process charcoal.
(5) add the deionized water high-speed stirring 1h of its quality 0.8 times in mix reagent process charcoal, add potassium hydroxide according to alkali charcoal than 2:1, continue to stir 1h, put into nickel crucible, be then placed in retort furnace, be slowly warming up to 400 DEG C, constant temperature 1h; Continue to be warming up to 700 DEG C, constant temperature 1h, is down to room temperature, takes out the charcoal after activation, and deionized water wash is to neutral, and dehydration, 120 DEG C are dried to constant weight, obtain gac.
(6) take gac, Nano carbon fibers peacekeeping tetrafluoroethylene according to metering proportion 85:10:5, make electrode film, be pressed onto on nickel foam collector, dry, obtain activated carbon electrodes; Get two panels identical electrodes respectively as ultracapacitor positive and negative electrode, overlay in button shroud with water system barrier film, inject KOH electrolytic solution, make ultracapacitor.As shown in figs. 1-7.
Embodiment 2
(1) rice husk deionized water repeatedly washs, and removes the impurity such as silt, dehydration, and temperature 80 DEG C is dried to constant weight, pulverizes.
(2) a certain amount of rice husk puts into ceramic crucible, is then placed in Reaktionsofen, connects device for recovering tail gas; Venting air, continues to pass into argon gas, is warming up to 450 DEG C with 20 DEG C/min, and constant temperature 1h, is down to room temperature, takes out carbon precursor.
(3) according to alkali charcoal mass ratio 2:1 by carbon precursor reflux 3h in potassium hydroxide aqueous solution, deionized water dilute, dehydrate, obtain oxygenation pretreatment charcoal.
(4) 6g Potassium Persulphate is taken and 6g Vanadium Pentoxide in FLAKES joins in the 50ml vitriol oil, stir, slowly be warming up to 60 DEG C, add oxygenation pretreatment charcoal 3g, constant temperature 3h, dilute with the deionized water of mixing solutions 2 times of volumes, stir 3h, then use a large amount of deionized water wash, dehydration, temperature 50 C is dried to constant weight, obtains mix reagent process charcoal.
(5) add the deionized water high-speed stirring 1h of its quality 1 times in mix reagent process charcoal, add potassium hydroxide according to alkali charcoal than 4:1, continue to stir 1h, put into nickel crucible, be then placed in retort furnace, be slowly warming up to 400 DEG C, constant temperature 1h; Continue to be warming up to 700 DEG C, constant temperature 1h, is down to room temperature, takes out the charcoal after activation, and deionized water wash is to neutral, and dehydration, 120 DEG C are dried to constant weight, obtain gac.
(6) take gac, Nano carbon fibers peacekeeping tetrafluoroethylene according to metering proportion 85:10:5, make electrode film, be pressed onto on nickel foam collector, dry, obtain activated carbon electrodes; Get two panels identical electrodes respectively as ultracapacitor positive and negative electrode, overlay in button shroud with water system barrier film, inject KOH electrolytic solution, make ultracapacitor.
Embodiment 3
(1) rice husk deionized water repeatedly washs, and removes the impurity such as silt, dehydration, and temperature 80 DEG C is dried to constant weight, pulverizes.
(2) a certain amount of rice husk puts into ceramic crucible, is then placed in Reaktionsofen, connects device for recovering tail gas; Venting air, continues to pass into argon gas, is warming up to 380 DEG C with 20 DEG C/min, and constant temperature 1h, is down to room temperature, takes out carbon precursor.
(3) according to alkali charcoal mass ratio 3:1 by carbon precursor reflux 3h in potassium hydroxide aqueous solution, deionized water dilute, dehydrate, obtain oxygenation pretreatment charcoal.
(4) 12g Potassium Persulphate is taken and 12g Vanadium Pentoxide in FLAKES joins in the 60ml vitriol oil, add oxygenation pretreatment charcoal 3g, stir 12h, dilute with the deionized water of mixing solutions 3 times of volumes, stir 5h, then use a large amount of deionized water wash, dehydration, temperature 50 C is dried to constant weight, obtains mix reagent process charcoal.
(5) add the deionized water high-speed stirring 1h of its quality 1.5 times in mix reagent process charcoal, add potassium hydroxide according to alkali charcoal than 4:1, continue to stir 1h, put into nickel crucible, be then placed in retort furnace, be slowly warming up to 450 DEG C, constant temperature 1h; Continue to be warming up to 700 DEG C, constant temperature 1h, is down to room temperature, takes out the charcoal after activation, and deionized water wash is to neutral, and dehydration, 120 DEG C are dried to constant weight, obtain gac.
(6) take gac, Nano carbon fibers peacekeeping tetrafluoroethylene according to metering proportion 85:10:5, make electrode film, be pressed onto on nickel foam collector, dry, obtain activated carbon electrodes; Get two panels identical electrodes respectively as ultracapacitor positive and negative electrode, overlay in button shroud with water system barrier film, inject KOH electrolytic solution, make carbon electrode/carbon electrode aqueous super capacitor.
Claims (3)
1. the method for preparation of active carbon for ultracapacitor, comprise the pre-treatment of rice husk raw material, charing, pre-treatment, activation, aftertreatment, it is characterized in that, pre-treatment comprises alkaline reagents pre-treatment, mix reagent pre-treatment and water infiltration pre-treatment, and its concrete steps are as follows:
(1) alkaline reagents pre-treatment: rice husk raw material is at the aqueous solution of alkaline reagents and potassium hydroxide, sodium hydroxide a kind of and their combination, alkali charcoal mass ratio is reflux 2 ~ 24h in 1:1 ~ 3:1, washing, dry, obtain the pretreated carbon precursor of alkaline reagents;
(2) mix reagent pre-treatment: the carbon precursor of alkaline reagents process puts into mix reagent and sulfuric acid, persulphate or Vanadium Pentoxide in FLAKES soak 2 ~ 24h, then the deionized water dilution of 1 ~ 3 times of volume of carbon precursor and mix reagent is used, stir 1 ~ 5h, extremely neutral with deionized water wash again, drying, obtains the pretreated charcoal of mix reagent;
(3) water infiltration pre-treatment: after the pretreated charcoal of mix reagent and water high-speed stirring to water complete wetting, add activator Keep agitation 1 ~ 3h, obtain the pretreated charcoal of water infiltration.
2. a kind of method for preparation of active carbon for ultracapacitor according to claim 1, is characterized in that described carbon precursor every gram sulfuric acid is 10 ~ 30ml, persulphate 1 ~ 5g used, Vanadium Pentoxide in FLAKES 1 ~ 10g used.
3. a kind of method for preparation of active carbon for ultracapacitor according to claim 1, is characterized in that infiltration water is 0.8 ~ 1.5 times of the pretreated carbonaceous amount of mix reagent.
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