CN107644742A - A kind of method that biogas residue activated carbon prepares ultracapacitor after dry fermentation based on biomass anaerobic - Google Patents
A kind of method that biogas residue activated carbon prepares ultracapacitor after dry fermentation based on biomass anaerobic Download PDFInfo
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Abstract
The invention discloses the method that biogas residue activated carbon after a kind of dry fermentation based on biomass anaerobic prepares ultracapacitor, this method is by after biogas residue pretreatment after biomass anaerobic dry fermentation, again through high temperature cabonization and activation, gained activation products obtain the activated carbon as electrode material for super capacitor after acid soak, washing, drying.Activated carbon prepared by the present invention has the pore structure that micro- mesopore is combined, higher specific surface area, while has higher specific capacitance and cyclical stability, is a kind of electrode material for super capacitor of relative ideal.The present invention prepares ultracapacitor using biogas residue, and then realizes the higher value application of biogas residue, and gained activated carbon structure is stable, hole is flourishing, has higher specific capacitance and cyclical stability, is a kind of electrode material for super capacitor of relative ideal.
Description
Technical field
The present invention relates to electrochemical field, and in particular to after one kind is based on biomass anaerobic dry fermentation prepared by biogas residue activated carbon
The method of ultracapacitor.
Background technology
China is large agricultural country, and the annual agricultural solid residue that produces is about more than 40 hundred million tons, and wherein fowl and animal excrement is more than 30
Hundred millionth, agricultural crop straw total amount be 700,000,000 tons, vegetable castoff be hundred million tons of 1-1.5.These discarded objects be both serious pollution sources and
Valuable biomass energy.But nowadays these discarded objects are mostly arbitrarily to be burned, abandoned or be directly discharged in environment, are made
Into the waste for causing resource while environmental pollution again.How effectively to handle agricultural wastes turn into must face both at home and abroad
Great environmental problem.
At present, anaerobic fermentation technology is one of agricultural wastes application technology as the second resource of domestic and international comparative maturity.The party
Method makes stalk carry out biofermentation under controlled conditions, produces biogas etc., and during need not supply oxygen and big energy,
And can be by the energy storage of fermented material 90% in methane.Anaerobic fermentation technology is divided into anaerobism wet fermentation and anaerobic dry hair
Ferment.Compared with anaerobism wet fermentation, anaerobic dry fermentation has using water wisely, convenient management, raising volume yield rate, processing cost low
The advantages that, at the same biogas slurry fermented yield is few, processing easily, non-secondary pollution, operating cost be low, process stabilization.But
The utilization ways of caused biogas residue are relatively limited during anaerobic dry fermentation, lack the conversion of high-valued product.Contain in biogas residue
The multiple elements such as organic matter, humic acid, N P and K, at the same also containing antibiotic, herbicide, agrochemical difficult degradation organic dirt
Thing is contaminated, still there is part residual in final product.The current utilization of biogas residue mainly divides aquaculture and land use, but biogas residue
Aquaculture using being more and more restricted because of the consideration of food security.Because the use of various additives is likely to cause natural pond
The hidden danger of pollution be present in the accumulation of heavy metal, antibiotic in slag, farmland ecosystem long-term use biogas residue.And biogas residue is utilized to prepare
The research of chemical raw material or energy products is seldom, it is only a small amount of using biogas residue prepare ethanol (agricultural mechanical journal, 2015,46
(5)：156-163), biodiesel (Biotechnol Biofuels, 2016, (9):253), biological pesticide (agricultural engineering
Report, 2013,29 (8)：Research report 212-217), has a disadvantage in that the yield of product is relatively low, and preparation technology still can
Produce discarded biogas residue.So how efficient utilize with processing biogas residue is more interesting issue at present.
Because cellulose containing not decomposed raw material and difficult degradation in biogas residue etc., and cellulose and lignin can be made
To prepare the good raw material of micropore biological matter carbon material.Patent CN103839699A is disclosed one kind and prepared using bagasse
The method of ultracapacitor carbon aerogels.Patent CN104576077A discloses a kind of system of graphene/Lignin-Based Activated Carbon
Method that is standby and being applied in ultracapacitor.Patent CN105819416A disclose a kind of bio-based porous carbon preparation and its
In the method applied in ultracapacitor.For biomass carbon material because its raw material is extensive, substantial amounts of oxygen-containing official is contained on its surface
Can group, the advantages that extra fake capacitance can be provided, turn into the important sources of carbon material.
The content of the invention
Biogas residue is active after being simply based on biomass anaerobic dry fermentation the invention provides a kind of cheap, synthesis technique
The method that charcoal prepares ultracapacitor, it is intended to while making the biogas residue rationally be utilized, obtain Stability Analysis of Structures, high conductivity, hole
The flourishing high performance electrode material of gap.
To solve technical problem, the present invention adopts the following technical scheme that：
The method that the present invention prepares ultracapacitor based on biogas residue activated carbon after biomass anaerobic dry fermentation, its spy is,
Comprise the following steps：
(1) biogas residue after biomass collection anaerobic dry fermentation, washed by deionized water, the method for acid soak or alkali immersion is entered
Row pretreatment, then dries 10-12h at 100-105 DEG C, crushed 40-100 mesh sieves, obtain standby biogas residue particle；
Or：Biogas residue after biomass collection anaerobic dry fermentation, washed by deionized water, the method for acid soak or alkali immersion is entered
Row pretreatment, then 100-105 DEG C dry 10-12h, add account for drying after biogas residue quality 0.1%-2% ferriferous oxide,
40-100 mesh sieves are crushed, obtain standby biogas residue particle；
(2) standby biogas residue particle obtained by step (1) is placed in high temperature process furnances, under inert gas shielding, with 2-15
DEG C/min heating rate is warming up to 350-550 DEG C, constant temperature carbonization 0.5-2h, then stop heating, continue to protect in inert gas
Room temperature is cooled under shield, takes out and is ground into powdery, obtains carbonized stock powder；
(3) by carbonized stock powder obtained by step (2) and activator in mass ratio 1:1-4 is mixed, then addition and carbonized stock
Powder quality volume ratio is 1g:30~150mL deionized water, ultrasonic disperse is uniform, then the heating water bath 10-12h at 80 DEG C,
It is finally putting into drying box at 100 DEG C and dries 2-3h；
Products therefrom is placed in high temperature process furnances, under inert gas shielding, is risen to 2-15 DEG C/min heating rate
650-900 DEG C, constant temperature activation 0.5-2h, then stop heating, continue to be cooled to room temperature under inert gas shielding, activated
Product；
(4) activation products obtained by step (3) are placed in concentrated acid, ultrasound immersion 10-30min, then with 80 DEG C of deionizations
Water washing is to neutrality, then product is placed in baking oven at 100 DEG C and dries 10-12h, finally crosses 200-400 mesh sieves, that is, is used as
The activated carbon of electrode material for super capacitor；
(5) by activated carbon obtained by step (4) and conductive agent and binding agent 7-9 in mass ratio：1-2：1-2 is mixed, and is added dropwise suitable
Measure organic solvent and ultrasonic disperse is uniform, obtain coating liquid；Gained coating liquid is uniformly applied on collector with plates for screen printing,
12-14h is dried in vacuo at 90-100 DEG C, finally by tablet press machine in 10-15MPa lower sheeting 10-30s, i.e., obtained super capacitor
Device electrode slice.
Wherein：
Step (1) described biomass can be maize straw or rice husk etc..
Acid soak described in step (1) is that biogas residue is added in the dilute sulfuric acid that mass concentration is 0.5%-2% to soak 2-
5h, then with deionized water rinsing to neutrality；The alkali immersion is the hydroxide that biogas residue is added to that mass concentration is 20%-30%
2-5h is soaked in sodium solution, then with deionized water rinsing to neutrality.
Ferriferous oxide described in step (1) is limonite.
Inert gas described in step (2) and (3) can be high pure nitrogen, high-purity argon gas or carbon dioxide, be preferably height
Pure nitrogen gas.
Activator described in step (3) is analysis pure cerium hydroxide potassium, analyzed in pure cerium hydroxide sodium, phosphoric acid or zinc chloride
At least one solid powder, preferably analyze pure cerium hydroxide potassium solid powder.
Concentrated acid described in step (4) is concentrated nitric acid or concentrated hydrochloric acid, preferably concentrated hydrochloric acid；The mass concentration of the concentrated acid is
20%-37.5%.
In step (5)：The conductive agent is chosen as acetylene black, carbon black or graphite etc., preferably acetylene black；The binding agent
It is chosen as PVDF or PTFE, preferably PVDF；The organic solvent is chosen as absolute ethyl alcohol or 1-METHYLPYRROLIDONE, is preferably
N- methyl adjoins pyrrolidone；The collector is chosen as copper foil, aluminium foil, nickel foam or carbon paper, preferably nickel foam.
Compared with the prior art, beneficial effects of the present invention are embodied in：
1st, the present invention prepares ultracapacitor using biogas residue, and then realizes the higher value application of biogas residue, and in calcining
During the material of difficult degradation can also be removed, played the productive potentialities and Environmental Effect of anaerobic dry fermentation technology to greatest extent
Benefit；And gained activated carbon structure is stable, hole is flourishing, has higher specific capacitance and cyclical stability, is a kind of relative ideal
Electrode material for super capacitor.
2nd, operating method simple possible of the invention, reaction condition is relatively mild, and energy-conserving and environment-protective, aftertreatment technology is simple,
It is repeated high.
Brief description of the drawings
Fig. 1 is the preparation technology schematic diagram of activated carbon of the present invention.
Embodiment
The method of the present invention is illustrated below by embodiment, the description of this part is only explanatory and shown
Plasticity, described example are only a part of example of the present invention, rather than whole examples, and the present invention does not limit to
In this.
Embodiment 1
The present embodiment prepares ultracapacitor as follows：
(1) biogas residue after the biomass anaerobic dry fermentation being collected into is washed with deionized, then dried at 105 DEG C
10h, 40 mesh sieves are crushed, obtain standby biogas residue particle.
(2) standby biogas residue particle obtained by 10g steps (1) is taken to be placed in quartz boat and be put into high temperature process furnances, in inertia
Under the GN 2 gas shielded, 400 DEG C are warming up to 10 DEG C/min heating rate, constant temperature carbonization 0.5h, then stops heating, continues
Room temperature is cooled under inert gas shielding, takes out and is ground into powdery, obtains carbonized stock powder；
(3) carbonized stock powder and 12g solid powder KOH obtained by 3g steps (2) are taken and is dissolved in 100mL deionized waters,
Then ultrasonic disperse is uniform, then the heating water bath 10h at 80 DEG C, is finally putting into drying box and 2h is dried at 100 DEG C；
Products therefrom is placed in quartz boat and is put into high temperature process furnances, inert nitrogen gas protection under, with 10 DEG C/
Min heating rate rises to 700 DEG C, constant temperature activation 50min, then stops heating, continues to be cooled under inert gas shielding
Room temperature, obtain activation products；
(4) activation products obtained by step (3) are placed in the concentrated hydrochloric acid that mass concentration is 37.5%, are with rated power
100W ultrasonic machine ultrasound immersion 15min, is then placed in baking oven with the constantly washing of 80 DEG C of deionized waters to neutrality, then by product
10h is dried at 100 DEG C, 200 mesh sieves is finally crossed, that is, obtains the activated carbon as electrode material for super capacitor；Synthetic route chart
See Fig. 1.
After tested, the specific surface area 2560m of activated carbon obtained by the present embodiment2g-1, total pore volume 0.96cm3g-1, aperture point
Cloth is narrow, based on mesopore and micropore distribution.
(5) by activated carbon obtained by step (4) and conductive agent acetylene black and binding agent PVDF in mass ratio 8：1：1 mixing, then
Appropriate 1-METHYLPYRROLIDONE, and the ultrasonic machine ultrasound 45min for being 100W with rated power are added, obtains coating liquid；Use silk screen
It is 1cm that gained coating liquid is uniformly applied to area by printed panel2Collector nickel foam on, 12h is dried in vacuo at 100 DEG C, most
Afterwards by tablet press machine in 12MPa lower sheeting 30s, i.e., obtained super capacitor electrode slice.
Using three-electrode system, electrolyte is 6M KOH solutions, the present embodiment institute on electrochemical workstation CHI660
Super capacitor electrode slice is obtained to be tested.After tested, the present embodiment the electrode obtained piece corresponds to difference and sweeps cyclic voltammetric under speed
Curve is in class rectangle shape, and it is the double layer capacitor of typical carbon material to show it, and its specific capacitance is 345Fg-1.Carry out charge and discharge electrical measurement
Examination, it is found that curve is in symmetrical triangle, illustrate the charge transfer reaction there occurs electric double layer, be 1Ag in current density-1When,
Specific capacitance corresponding to absorbent charcoal material is 208Fg-1。
Embodiment 2
The present embodiment prepares ultracapacitor as follows：
(1) dilute sulfuric acid that biogas residue mass concentration after the biomass anaerobic dry fermentation being collected into is 0.75% is soaked and stirred
Even processing 3h, then constantly washed to neutrality with deionized water, 10h then is dried at 105 DEG C, crushed 40 mesh sieves, is obtained standby
With biogas residue particle；
(2) standby biogas residue particle obtained by 10g steps (1) is taken to be placed in quartz boat and be put into high temperature process furnances, in inertia
Under the GN 2 gas shielded, 400 DEG C are warming up to 10 DEG C/min heating rate, constant temperature carbonization 0.5h, then stops heating, continues
Room temperature is cooled under inert gas shielding, takes out and is ground into powdery, obtains carbonized stock powder；
(3) carbonized stock powder and 12g activator KOH obtained by 3g steps (2) are taken and is dissolved in 100mL deionized waters, so
Ultrasonic disperse is uniform afterwards, then the heating water bath 10h at 80 DEG C, is finally putting into drying box and 2h is dried at 100 DEG C；
Products therefrom is placed in quartz boat and is put into high temperature process furnances, inert nitrogen gas protection under, with 10 DEG C/
Min heating rate rises to 700 DEG C, constant temperature activation 50min, then stops heating, continues to be cooled under inert gas shielding
Room temperature, obtain activation products；
(4) activation products obtained by step (3) are placed in the concentrated hydrochloric acid that mass concentration is 37.5%, are with rated power
100W ultrasonic machine ultrasound immersion 15min, is then placed in baking oven with the constantly washing of 80 DEG C of deionized waters to neutrality, then by product
10h is dried at 100 DEG C, 200 mesh sieves is finally crossed, that is, obtains the activated carbon as electrode material for super capacitor.
After tested, the specific surface area 3230m of activated carbon obtained by the present embodiment2g-1, total pore volume 1.5cm3g-1, pore-size distribution
It is narrow, based on mesopore and micropore distribution.
(5) by activated carbon obtained by step (4) and conductive agent acetylene black and binding agent PVDF in mass ratio 8：1：1 mixing, then
Appropriate 1-METHYLPYRROLIDONE, and the ultrasonic machine ultrasound 45min for being 100W with rated power are added, obtains coating liquid；Use silk screen
It is 1cm that gained coating liquid is uniformly applied to area by printed panel2Collector nickel foam on, 12h is dried in vacuo at 100 DEG C, most
Afterwards by tablet press machine in 12MPa lower sheeting 30s, i.e., obtained super capacitor electrode slice.
Tested by the identical method of embodiment 1.After tested, the present embodiment the electrode obtained piece corresponds to difference and swept under speed
Cyclic voltammetry curve is in class rectangle shape, and it is the double layer capacitor of typical carbon material to show it, and its specific capacitance is 435Fg-1.Carry out
Charge-discharge test, it is found that curve is in symmetrical triangle, illustrate the charge transfer reaction there occurs electric double layer, be in current density
1Ag-1When, specific capacitance corresponding to absorbent charcoal material is 306Fg-1。
Embodiment 3
The present embodiment prepares ultracapacitor as follows：
(1) sodium hydroxide solution that biogas residue mass concentration after the biomass anaerobic dry fermentation being collected into is 20% is soaked
And processing 3h is stirred evenly, then constantly washed to neutrality with deionized water, 10h then is dried at 105 DEG C, 40 mesh sieves is crushed, obtains
Obtain standby biogas residue particle.
(2) standby biogas residue particle obtained by 10g steps (1) is taken to be placed in quartz boat and be put into high temperature process furnances, in inertia
Under the GN 2 gas shielded, 400 DEG C are warming up to 10 DEG C/min heating rate, constant temperature carbonization 0.5h, then stops heating, continues
Room temperature is cooled under inert gas shielding, takes out and is ground into powdery, obtains carbonized stock powder；
(3) carbonized stock powder and 12g KOH solid powders obtained by 3g steps (2) are taken and are dissolved in 100mL deionized waters,
Then ultrasonic disperse is uniform, then the heating water bath 10h at 80 DEG C, is finally putting into drying box and 2h is dried at 100 DEG C；
Products therefrom is placed in quartz boat and is put into high temperature process furnances, inert nitrogen gas protection under, with 10 DEG C/
Min heating rate rises to 700 DEG C, constant temperature activation 50min, then stops heating, continues to be cooled under inert gas shielding
Room temperature, obtain activation products；
(4) activation products obtained by step (3) are placed in the concentrated hydrochloric acid that mass concentration is 37.5%, are with rated power
100W ultrasonic machine ultrasound immersion 15min, is then placed in baking oven with the constantly washing of 80 DEG C of deionized waters to neutrality, then by product
10h is dried at 100 DEG C, 200 mesh sieves is finally crossed, that is, obtains the activated carbon as electrode material for super capacitor.
After tested, the specific surface area 2880m of activated carbon obtained by the present embodiment2g-1, total pore volume 1.2cm3g-1, pore-size distribution
It is narrow, based on mesopore and micropore distribution.
(5) by activated carbon obtained by step (4) and conductive agent acetylene black and binding agent PVDF in mass ratio 8：1：1 mixing, then
Appropriate 1-METHYLPYRROLIDONE, and the ultrasonic machine ultrasound 45min for being 100W with rated power are added, obtains coating liquid；Use silk screen
It is 1cm that gained coating liquid is uniformly applied to area by printed panel2Collector nickel foam on, 12h is dried in vacuo at 100 DEG C, most
Afterwards by tablet press machine in 12MPa lower sheeting 30s, i.e., obtained super capacitor electrode slice.
Tested by the identical method of embodiment 1.After tested, the present embodiment the electrode obtained piece corresponds to difference and swept under speed
Cyclic voltammetry curve is in class rectangle shape, and it is the double layer capacitor of typical carbon material to show it, and its specific capacitance is 394Fg-1.Carry out
Charge-discharge test, it is found that curve is in symmetrical triangle, illustrate the charge transfer reaction there occurs electric double layer, be in current density
1Ag-1When, specific capacitance corresponding to absorbent charcoal material is 235Fg-1。
Embodiment 4
(1) biogas residue after the biomass anaerobic dry fermentation being collected into is washed with deionized, then dried at 105 DEG C
10h, add account for drying after biogas residue quality 0.1% limonite, crushed 40 mesh sieves, obtain standby biogas residue particle.
(2) standby biogas residue particle obtained by 10g steps (1) is taken to be placed in quartz boat and be put into high temperature process furnances, in inertia
Under the GN 2 gas shielded, 400 DEG C are warming up to 10 DEG C/min heating rate, constant temperature carbonization 0.5h, then stops heating, continues
Room temperature is cooled under inert gas shielding, takes out and is ground into powdery, obtains carbonized stock powder；
(3) carbonized stock powder and 12g solid powder obtained by 3g steps (2) are taken and is dissolved in 100mL deionized waters, then
Ultrasonic disperse is uniform, then the heating water bath 10h at 80 DEG C, is finally putting into drying box and 2h is dried at 100 DEG C；
Products therefrom is placed in quartz boat and is put into high temperature process furnances, inert nitrogen gas protection under, with 10 DEG C/
Min heating rate rises to 700 DEG C, constant temperature activation 50min, then stops heating, continues to be cooled under inert gas shielding
Room temperature, obtain activation products；
(4) activation products obtained by step (3) are placed in the concentrated hydrochloric acid that mass concentration is 37.5%, are with rated power
100W ultrasonic machine ultrasound immersion 15min, is then placed in baking oven with the constantly washing of 80 DEG C of deionized waters to neutrality, then by product
10h is dried at 100 DEG C, 200 mesh sieves is finally crossed, that is, obtains the activated carbon as electrode material for super capacitor.
After tested, the specific surface area 2710m of activated carbon obtained by the present embodiment2g-1, total pore volume 0.99cm3g-1, aperture point
Cloth is narrow, based on mesopore and micropore distribution.
(5) by activated carbon obtained by step (4) and conductive agent acetylene black and binding agent PVDF in mass ratio 8：1：1 mixing, then
Appropriate 1-METHYLPYRROLIDONE, and the ultrasonic machine ultrasound 45min for being 100W with rated power are added, obtains coating liquid；Use silk screen
It is 1cm that gained coating liquid is uniformly applied to area by printed panel2Collector nickel foam on, 12h is dried in vacuo at 100 DEG C, most
Afterwards by tablet press machine in 12MPa lower sheeting 30s, i.e., obtained super capacitor electrode slice.
Tested by the identical method of embodiment 1.After tested, the present embodiment the electrode obtained piece corresponds to difference and swept under speed
Cyclic voltammetry curve is in class rectangle shape, and it is the double layer capacitor of typical carbon material to show it, and its specific capacitance is 356Fg-1.Carry out
Charge-discharge test, it is found that curve is in symmetrical triangle, illustrate the charge transfer reaction there occurs electric double layer, be in current density
1Ag-1When, specific capacitance corresponding to absorbent charcoal material is 217Fg-1。
Embodiment 5
(1) dilute sulfuric acid that biogas residue mass concentration after the biomass anaerobic dry fermentation being collected into is 0.75% is soaked and stirred
Even processing 3h, then constantly washed to neutrality with deionized water, then dries 10h at 105 DEG C, adds and accounts for biogas residue matter after drying
The limonite of amount 0.1%, crushed 40 mesh sieves, obtains standby biogas residue particle；
(2) standby biogas residue particle obtained by 10g steps (1) is taken to be placed in quartz boat and be put into high temperature process furnances, in inertia
Under the GN 2 gas shielded, 400 DEG C are warming up to 10 DEG C/min heating rate, constant temperature carbonization 0.5h, then stops heating, continues
Room temperature is cooled under inert gas shielding, takes out and is ground into powdery, obtains carbonized stock powder；
(3) carbonized stock powder and 12g solid powder obtained by 3g steps (2) are taken and is dissolved in 100mL deionized waters, then
Ultrasonic disperse is uniform, then the heating water bath 10h at 80 DEG C, is finally putting into drying box and 2h is dried at 100 DEG C；
Products therefrom is placed in quartz boat and is put into high temperature process furnances, inert nitrogen gas protection under, with 10 DEG C/
Min heating rate rises to 700 DEG C, constant temperature activation 50min, then stops heating, continues to be cooled under inert gas shielding
Room temperature, obtain activation products；
(4) activation products obtained by step (3) are placed in the concentrated hydrochloric acid that mass concentration is 37.5%, are with rated power
100W ultrasonic machine ultrasound immersion 15min, is then placed in baking oven with the constantly washing of 80 DEG C of deionized waters to neutrality, then by product
10h is dried at 100 DEG C, 200 mesh sieves is finally crossed, that is, obtains the activated carbon as electrode material for super capacitor.
After tested, the specific surface area 3400m of activated carbon obtained by the present embodiment2g-1, total pore volume 1.7cm3g-1, pore-size distribution
It is narrow, based on mesopore and micropore distribution.
(5) by activated carbon obtained by step (4) and conductive agent acetylene black and binding agent PVDF in mass ratio 8：1：1 mixing, then
Appropriate 1-METHYLPYRROLIDONE, and the ultrasonic machine ultrasound 45min for being 100W with rated power are added, obtains coating liquid；Use silk screen
It is 1cm that gained coating liquid is uniformly applied to area by printed panel2Collector nickel foam on, 12h is dried in vacuo at 100 DEG C, most
Afterwards by tablet press machine in 12MPa lower sheeting 30s, i.e., obtained super capacitor electrode slice.
Tested by the identical method of embodiment 1.After tested, the present embodiment the electrode obtained piece corresponds to difference and swept under speed
Cyclic voltammetry curve is in class rectangle shape, and it is the double layer capacitor of typical carbon material to show it, and its specific capacitance is 450Fg-1.Carry out
Charge-discharge test, it is found that curve is in symmetrical triangle, illustrate the charge transfer reaction there occurs electric double layer, be in current density
1Ag-1When, specific capacitance corresponding to absorbent charcoal material is 320Fg-1。
Embodiment 6
(1) sodium hydroxide solution that biogas residue mass concentration after the biomass anaerobic dry fermentation being collected into is 20% is soaked
And processing 3h is stirred evenly, then constantly washed to neutrality with deionized water, then dry 10h at 105 DEG C, added and account for natural pond after drying
The limonite of slag amount 0.1%, 40 mesh sieves are crushed, obtain standby biogas residue particle.
(2) standby biogas residue particle obtained by 10g steps (1) is taken to be placed in quartz boat and be put into high temperature process furnances, in inertia
Under the GN 2 gas shielded, 400 DEG C are warming up to 10 DEG C/min heating rate, constant temperature carbonization 0.5h, then stops heating, continues
Room temperature is cooled under inert gas shielding, takes out and is ground into powdery, obtains carbonized stock powder；
(3) carbonized stock powder and 12g solid powder obtained by 3g steps (2) are taken and is dissolved in 100mL deionized waters, then
Ultrasonic disperse is uniform, then the heating water bath 10h at 80 DEG C, is finally putting into drying box and 2h is dried at 100 DEG C；
Products therefrom is placed in quartz boat and is put into high temperature process furnances, inert nitrogen gas protection under, with 10 DEG C/
Min heating rate rises to 700 DEG C, constant temperature activation 50min, then stops heating, continues to be cooled under inert gas shielding
Room temperature, obtain activation products；
(4) activation products obtained by step (3) are placed in the concentrated hydrochloric acid that mass concentration is 37.5%, are with rated power
100W ultrasonic machine ultrasound immersion 15min, is then placed in baking oven with the constantly washing of 80 DEG C of deionized waters to neutrality, then by product
10h is dried at 100 DEG C, 200 mesh sieves is finally crossed, that is, obtains the activated carbon as electrode material for super capacitor.
After tested, the specific surface area 3100m of activated carbon obtained by the present embodiment2g-1, total pore volume 1.4cm3g-1, pore-size distribution
It is narrow, based on mesopore and micropore distribution.
(5) by activated carbon obtained by step (4) and conductive agent acetylene black and binding agent PVDF in mass ratio 8：1：1 mixing, then
Appropriate 1-METHYLPYRROLIDONE, and the ultrasonic machine ultrasound 45min for being 100W with rated power are added, obtains coating liquid；Use silk screen
It is 1cm that gained coating liquid is uniformly applied to area by printed panel2Collector nickel foam on, 12h is dried in vacuo at 100 DEG C, most
Afterwards by tablet press machine in 12MPa lower sheeting 30s, i.e., obtained super capacitor electrode slice.
Tested by the identical method of embodiment 1.After tested, the present embodiment the electrode obtained piece corresponds to difference and swept under speed
Cyclic voltammetry curve is in class rectangle shape, and it is the double layer capacitor of typical carbon material to show it, and its specific capacitance is 400Fg-1.Carry out
Charge-discharge test, it is found that curve is in symmetrical triangle, illustrate the charge transfer reaction there occurs electric double layer, be in current density
1Ag-1When, specific capacitance corresponding to absorbent charcoal material is 250Fg-1。
Claims (8)
1. a kind of method that biogas residue activated carbon prepares ultracapacitor after dry fermentation based on biomass anaerobic, it is characterised in that bag
Include following steps：
(1) biogas residue after biomass collection anaerobic dry fermentation, washed by deionized water, the method for acid soak or alkali immersion is carried out in advance
Processing, 10-12h then is dried at 100-105 DEG C, 40-100 mesh sieves is crushed, obtains standby biogas residue particle；
Or：Biogas residue after biomass collection anaerobic dry fermentation, washed by deionized water, the method for acid soak or alkali immersion is carried out in advance
Processing, then 100-105 DEG C dry 10-12h, add account for drying after biogas residue quality 0.1%-2% ferriferous oxide, crush
40-100 mesh sieves are crossed, obtain standby biogas residue particle；
(2) standby biogas residue particle obtained by step (1) is placed in high temperature process furnances, under inert gas shielding, with 2-15 DEG C/
Min heating rate is warming up to 350-550 DEG C, constant temperature carbonization 0.5-2h, then stops heating, continues under inert gas shielding
Room temperature is cooled to, takes out and is ground into powdery, obtains carbonized stock powder；
(3) by carbonized stock powder obtained by step (2) and activator in mass ratio 1:1-4 is mixed, and is then added and carbonized stock powder
Mass volume ratio is 1g:30~150mL deionized water, ultrasonic disperse is uniform, then the heating water bath 10-12h at 80 DEG C, finally
It is put into drying box at 100 DEG C and dries 2-3h；
Products therefrom is placed in high temperature process furnances, and under inert gas shielding, 650- is risen to 2-15 DEG C/min heating rate
900 DEG C, constant temperature activation 0.5-2h, then stop heating, continue to be cooled to room temperature under inert gas shielding, obtain activation production
Thing；
(4) activation products obtained by step (3) are placed in concentrated acid, ultrasound immersion 10-30min, then washed with 80 DEG C of deionizations
Wash to neutrality, then product is placed in baking oven at 100 DEG C and dries 10-12h, finally cross 200-400 mesh sieves, that is, obtain as super
The activated carbon of capacitor electrode material；
(5) by activated carbon obtained by step (4) and conductive agent and binding agent 7-9 in mass ratio：1-2：1-2 is mixed, and dropwise addition has in right amount
Simultaneously ultrasonic disperse is uniform for solvent, obtains coating liquid；Gained coating liquid is uniformly applied on collector with plates for screen printing, 90-
12-14h is dried in vacuo at 100 DEG C, finally by tablet press machine in 10-15MPa lower sheeting 10-30s, i.e., obtained super capacitor electrode
Pole piece.
2. according to the method for claim 1, it is characterised in that：Biomass described in step (1) is maize straw or rice husk.
3. according to the method for claim 1, it is characterised in that：Acid soak is that biogas residue is added into matter described in step (1)
Amount concentration is to soak 2-5h in 0.5%-2% dilute sulfuric acids, then with deionized water rinsing to neutrality；The alkali immersion is by biogas residue
It is added in the sodium hydroxide solution that mass concentration is 20%-30% and soaks 2-5h, then with deionized water rinsing to neutrality.
4. according to the method for claim 1, it is characterised in that：Ferriferous oxide described in step (1) is limonite.
5. according to the method for claim 1, it is characterised in that：The inert gas is high pure nitrogen, high-purity argon gas or two
Carbonoxide.
6. according to the method for claim 1, it is characterised in that：Activator described in step (3) is potassium hydroxide, hydroxide
At least one of sodium, phosphoric acid or zinc chloride.
7. according to the method for claim 1, it is characterised in that：Concentrated acid described in step (4) is concentrated nitric acid or concentrated hydrochloric acid；Institute
The mass concentration for stating concentrated acid is 20-37.5%.
8. according to the method for claim 1, it is characterised in that：In step (5), the conductive agent be acetylene black, carbon black or
Graphite, the binding agent are PVDF or PTFE, and the organic solvent is absolute ethyl alcohol or 1-METHYLPYRROLIDONE, the collector
For copper foil, aluminium foil, nickel foam or carbon paper.
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