CN106185920B - A kind of porous carbon materials and its preparation method and application - Google Patents
A kind of porous carbon materials and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of porous carbon materials and its preparation method and application.Lignin in the black liquid that the present invention is generated using the alkali paper-making containing KOH is carbon source, preprocessed, carbonization and activation, during the activation, KOH in black liquid plays the role of activator, the porous carbon materials with high-specific surface area are obtained, specific surface area is 1500~3000m2/ g, pore-size distribution is 0.5~3nm, based on micropore (50~80%), supplemented by mesoporous (20~50%), ultracapacitor as electrode material assembling has good chemical property and cycle performance, specific capacitance is up to 337F/g, and after 3000 Xun Huans, capacitance is maintained at more than 98%.Preparation method provided by the invention is easy to operate, mild condition, low energy consumption, of low cost, technique is easily-controllable, is promoted suitable for large-scale industry.
Description
Technical field
The present invention relates to technical field of function materials, more particularly to a kind of porous carbon materials and its preparation method and application.
Background technology
Ultracapacitor is also known as electrochemical capacitor, has the spies such as fast charging and discharging, power density are big, have extended cycle life
Point.Based on these excellent performances, ultracapacitor can be used as free of contamination backup power supply to be used for a variety of electrical equipments, simultaneously
It can also collectively constitute composite power source with battery and provide power for electric vehicle, receive significant attention and quickly sent out in recent years
Exhibition.
Ultracapacitor be different from traditional electrochmical power source, be one kind between traditional capacitor and battery, have spy
The power supply of different performance, relies primarily on electric double layer and redox fake capacitance charge storage electric energy, but its energy storage process not
It chemically reacts, this thermal energy storage process is reversible.Its basic principle is all as the double layer capacitor of other species
The double electrical layers formed using activated carbon porous electrode and electrolyte obtain the capacity of super large.
In the prior art, porous carbon materials are mostly prepared as carbon source using starch, polymer etc..In generation, inspires and reports one
The method that kind prepares porous carbon materials using starch as carbon source, (generation inspiration prepares the research of porous carbon materials using starch as presoma
[D] Guangxi Normal Universitys, 2008.)；A kind of polymer carbon materials are disclosed in the Chinese patent of Publication No. CN104086678A
The preparation method of material, and specifically disclose with alkali or alkaline earth metal and polyalkenyl halides, halogenated polyolefin, polyhalohydrocarbon or
Porous carbon materials are prepared for raw material in its derivative.But the cost of material of the above method is higher, and preparation method is complicated.
The boiling in paper mill now is generally dissolved out using chemicals, the reaction process of removing lignin, by the lignin of straw
Low molecule lignin is degraded into, the ability for adding the dissolution of lignin and being extracted, so as to fulfill lignin and cellulose, hemicellulose
Separation.It is pretreated black liquor that can generate some waste liquids during using oxygenation pretreatment.Under normal conditions, black liquor is straight
Run in into sewage treatment plant, can so greatly increase the expenses of environmental protection of sewage disposal.
The content of the invention
It is an object of the invention to provide a kind of porous carbon materials and its preparation method and application.Preparation provided by the invention
Method is of low cost, and the porous carbon materials of preparation have big specific surface area, has good chemical property available for preparing
Ultracapacitor.
The present invention provides a kind of preparation methods of porous carbon materials, comprise the following steps：
(1) black liquid is pre-processed, obtains solid mixture, the black liquid contains for what alkali paper-making generated
There is the waste liquid of KOH；
(2) solid mixture that the step (1) obtains is carbonized, obtains carbon material；
(3) carbon material that the step (2) obtains is activated, obtains porous carbon materials.
Preferably, black liquid is mixed before pretreatment with melamine described in step (1), obtains mixed solution.
Preferably, the quality of the melamine is the 0.5~2% of black liquid quality.
Preferably, carbonization carries out under inert gas shielding in the step (2).
Preferably, the temperature of the carbonization is 350~450 DEG C, and the time of carbonization is 0.5~1.5h.
Preferably, activation carries out under inert gas shielding in the step (3).
Preferably, the temperature of the activation is 600~900 DEG C, and the time of activation is 0.5~1.5h.
The present invention also provides porous carbon materials prepared by preparation method described in above-mentioned technical proposal, the porous carbon materials
Specific surface area be 1500~3000m2/g。
Preferably, the aperture of the porous carbon materials is 0.5~3nm.
The present invention also provides application of the porous carbon materials described in above-mentioned technical proposal in ultracapacitor.
Lignin in the black liquid that the present invention is generated using the alkali paper-making containing KOH is carbon source, preprocessed, carbonization
And activation, during the activation, the KOH in black liquid plays the role of activator, obtains with high-specific surface area
Porous carbon materials.The experimental results showed that the specific surface area of porous carbon materials prepared by preparation method provided by the invention is
1500~3000m2/ g, pore-size distribution is 0.5~3nm, based on micropore (50~80%), supplemented by mesoporous (20~50%), is made
Ultracapacitor for electrode material assembling has good chemical property and cycle performance, specific capacitance up to 337F/g,
After 3000 Xun Huans, capacitance is maintained at more than 98%.
Preparation method provided by the invention is easy to operate, mild condition, low energy consumption, of low cost, technique is easily-controllable, suitable for big
Technical scale is promoted.
Description of the drawings
Fig. 1 is the SEM figures of the porous carbon materials obtained in embodiment 7；
Fig. 2 is the graph of pore diameter distribution of the porous carbon materials obtained in embodiment 7；
Fig. 3 is the SEM figures of the porous carbon materials obtained in embodiment 9；
Fig. 4 is the graph of pore diameter distribution of the porous carbon materials obtained in embodiment 9；
Fig. 5 is the cyclic voltammetry curve of the carbon electrode obtained in embodiment 10；
Fig. 6 is the constant current charge-discharge curve of the carbon electrode obtained in embodiment 10；
Fig. 7 is the SEM figures of the porous carbon materials obtained in embodiment 11；
Fig. 8 is the graph of pore diameter distribution of the porous carbon materials obtained in embodiment 11.
Specific embodiment
The present invention provides a kind of preparation methods of porous carbon materials, comprise the following steps：
(1) black liquid is pre-processed, obtains solid mixture, the black liquid contains for what alkali paper-making generated
There is the waste liquid of KOH；
(2) solid mixture that the step (1) obtains is carbonized, obtains carbon material；
(3) carbon material that the step (2) obtains is activated, obtains porous carbon materials.
For the present invention to be raw material in black liquid, the black liquid is the waste liquid containing KOH that alkali paper-making generates.
It is a kind of unbodied, molecule being widely present in plant rich in there is substantial amounts of lignin (Lignin) in black liquid
Armaticity high polymer containing oxo phenylpropanol or derivatives thereof structural unit in structure, by that can be obtained after carbonization and activation
High-quality carbon material；KOH in the black liquid, by being reacted in activation process with carbon, generates H as activator2、CO、
CO2Gases are waited, effective exploitation goes out mesoporous and microcellular structure.
Method provided by the invention can be raw material with the waste liquid that in papermaking enterprise, alkali paper-making technique generates, can also
Alkali paper-making process is simulated, voluntarily prepares black liquid.In the present invention, the preparation of the black liquid preferably includes following step
Suddenly：
(a) fibrous raw material with KOH solution is mixed, mixed material is obtained by the reaction；
(b) separation of solid and liquid is carried out to the mixed material that the step (a) obtains, obtains black liquid.
The present invention preferably mixes fibrous raw material with KOH solution, and mixed material is obtained by the reaction.In the present invention, the fibre
The mass ratio for tieing up raw material and KOH is preferably 1:0.2~0.8, more preferably 1:0.4~0.6.
The present invention does not have the species of the fibrous raw material and source special restriction, using known to those skilled in the art
Papermaking fibers raw material.In the present invention, the fibrous raw material is preferably plant fiber, more preferably straw, corn
One or more in stalk, wheat straw and timber.
In the present invention, the fibrous raw material is preferably pre-processed before use, obtains fiber dust.In the present invention
In, the pretreatment includes crushing and drying.The present invention does not have the equipment of the crushing special restriction, using this field skill
The equipment of comminuting matter known to art personnel.In the present invention, the crushing carries out preferably in pulverizer；The crushing
The granularity of fibrous raw material is preferably not lower than 40 mesh afterwards.
Preferably processing is dried in fibrous raw material after crushing by the present invention, obtains fiber dust.In the present invention, it is described
Dry temperature is preferably 100~110 DEG C, more preferably 103~107 DEG C；The time of the drying is preferably 11~13h, more
Preferably 11.5~12.5h.
In the present invention, the KOH is added preferably in the form of KOH solution, and the mass concentration of the KOH solution is preferably
2~8%, more preferably 4~6%.
The no special restriction of operation that the present invention mixes the fibrous raw material with KOH solution, using art technology
The technical solution of mixed material is prepared known to personnel.In the present invention, the mixing preferably carries out under agitation.
In the present invention, the rate of the stirring is preferably 100~800r/min, more preferably 300~500r/min, is most preferably
350~450r/min；The time of the stirring is preferably 2~6min, more preferably 3~5min.
The present invention does not have the device of the reaction special restriction, using reaction unit well known to those skilled in the art
.In the present invention, the reaction preferably carries out in a kettle；The reaction kettle is preferably stainless steel cauldron；It is described
The liner of reaction kettle is preferably polytetrafluoroethylene (PTFE).In the present invention, the temperature of the reaction is preferably 110~130 DEG C, more preferably
It it is most preferably 118~122 DEG C for 115~125 DEG C；The time of the reaction is preferably 4~6h, more preferably 4.5~5.5h.
In the present invention, in the reaction process, KOH solution dissolves out the lignin in fibrous raw material, obtains alkaline mixt material.
Mixed material progress cold bath is preferably cooled to room temperature by the present invention after the completion of reaction.In the present invention,
The cooldown rate is preferably 4~6 DEG C/min.
After the completion of the cooling, the mixed material that the present invention preferably obtains cooling separates, and obtains black liquid.
In the present invention, the separation is preferably to centrifuge；The rotating speed of the centrifugation is preferably 3500~4500r/min, more excellent
Elect 3800~4200r/min as.
After obtaining black liquid, the present invention preferably mixes the black liquid with melamine, obtains mixed solution.
In the present invention, the quality of the melamine is preferably the 0.2~5% of black liquid quality, and more preferably 0.5~2%.At this
In invention, the melamine part provides N for porous carbon materials, exists in carbon material surface with N-O key-shapeds formula as nitrogen source
, hydrogen bond can be formed in the electrolytic solution so that manufactured electrode material has good wettability and electric conductivity, so as to significantly
Improve capacitive effect；In addition, high-temperature lower part divides melamine to decompose, N can be generated2And salt, salt play the work of drilling after elution
With.
The no special restriction of operation that the present invention mixes the black liquid with melamine, using art technology
The operation of mixed solution is prepared known to personnel.In the present invention, the mixing preferably carries out under agitation；It is described
The rate of stirring is preferably 100~800r/min, more preferably 300~500r/min；The time of the stirring is preferably 2~
6min, more preferably 3~5min.
The present invention preferably before carbonization by the black liquid or mixed solution including black liquid and melamine into
Row pretreatment, obtains solid mixture.In the present invention, the pretreatment is preferably drying.In the present invention, the drying
Temperature is preferably 80~90 DEG C, more preferably 84~86 DEG C；The time of the drying is preferably 10~14h, more preferably 11~
13h。
After completing the pretreatment, obtained solid mixture is carbonized by the present invention, obtains carbon material.The present invention is excellent
Choosing is kept the temperature after the solid mixture is warming up to carburizing temperature, is carbonized.In the present invention, the temperature of the carbonization is preferred
For 350~450 DEG C, more preferably 380~420 DEG C；The time of the carbonization is preferably 0.5~1.5h, more preferably 0.8~
1.2h；The heating rate is preferably 1.5~2.5 DEG C/min.In the present invention, the carbonization is preferably under inert gas shielding
It carries out；The airflow rate of the inert gas is preferably 0.7~0.9L/min.
After obtaining the carbon material, the present invention activates the carbon material, obtains porous carbon materials.It is of the invention preferred
It keeps the temperature, is activated after the carbon material is warming up to activation temperature.In the present invention, the temperature of the activation is preferably 600
~900 DEG C, more preferably 700~800 DEG C are most preferably 730~760 DEG C；The time of the activation is preferably 0.5~1.5h,
More preferably 0.8~1.2h；The heating rate is preferably 4~6 DEG C/min.In the present invention, the activation is preferably in inertia
It is carried out under gas shield；The airflow rate of the inert gas is preferably 0.7~0.9L/min.In the present invention, the activation
KOH can effectively develop mesoporous and micropore in the process, and central hole structure provides the passage of diffusion for ion, and microcellular structure is favourable
In the adsorption desorption of ion, so that porous carbon materials have good capacitive properties.
To improve the purity of porous carbon materials, the present invention is washed and done to the obtained porous carbon materials that activate
It is dry.The present invention to the washing and the dry no special restriction of operation, using washing well known to those skilled in the art and
Dry technical solution.In the present invention, the detergent of the washing is preferably distilled water and ethyl alcohol.In the reality of the present invention
It applies in example, it is preferred to use distilled water and ethyl alcohol alternately wash；The distilled water and the number of ethyl alcohol washing are respectively preferably 2~4
It is secondary.In the present invention, the temperature of the drying is preferably 70~90 DEG C, more preferably 75~85 DEG C；The time of the drying is excellent
Elect 11~13h as, more preferably 11.5~12.5h.
The present invention also provides porous carbon materials prepared by preparation method described in above-mentioned technical proposal, the porous carbon materials
Specific surface area be 1500~3000m2/ g, more preferably 1800~2200m2/g.In the present invention, the porous carbon materials
Pore-size distribution is preferably 0.5~3nm, more preferably 1~2nm；In the porous carbon materials ratio of micropore be preferably 50~
80%, more preferably 60~70%；The ratio of mesoporous is preferably 20~50%, and more preferably 30~40%.In the present invention, institute
The passage that the central hole structure of porous carbon materials provides diffusion for ion is stated, microcellular structure is conducive to the adsorption desorption of ion, suitable
Mesoporous, microcellular structure ratio make electrode material have preferable capacitive properties.
In the present invention, form and count according to element, it is 75~90% that the porous carbon materials, which preferably include mass fraction,
Carbon, 5~20% oxygen and 1~6% nitrogen.In the present invention, the nitrogen and oxygen are distributed in porous carbon materials with N-O key-shaped formulas
Surface can form hydrogen bond in the electrolytic solution so that manufactured electrode material has good wettability and electric conductivity, improves electricity
Hold effect.
The present invention also provides application of the above-mentioned porous carbon materials in ultracapacitor, are preferably specifically used as super capacitor
The application of the carbon electrode of device.
In the present invention, the carbon electrode preferably includes porous carbon materials, conductive agent, binding agent and collector.In this hair
In bright, the mass ratio of the porous carbon materials, conductive agent and binding agent is preferably (6~10):(0.3~2):(0.3~2), more
Preferably (7~9):(0.5~1.5):(0.5~1.5).
The present invention does not have special restriction for the species of the conductive agent, using conduction well known to those skilled in the art
Agent.In the present invention, the conductive agent is preferably carbon black conductive agent, more preferably specifically includes acetylene black, electrically conductive graphite KS-
6 or Ketjen black.
The present invention does not have special restriction for the species of the binding agent, using bonding well known to those skilled in the art
Agent.In the present invention, the binding agent is preferably polytetrafluoroethylene (PTFE) or Kynoar.
The present invention does not have special restriction for the collector, is using collector well known to those skilled in the art
It can.In the present invention, the collector preferably includes nickel foam.
The present invention does not have special restriction for the preparation method of the carbon electrode, and use is well known to those skilled in the art
Prepare the technical solution of carbon electrode.In the present invention, the preparation method of the carbon electrode preferably includes following steps：
Porous carbon materials with conductive agent, binding agent and ethyl alcohol are mixed, obtain mixed material；
By mixed material coating on a current collector, it is dried to obtain carbon electrode.
The present invention mixes the porous carbon materials with conductive agent, binding agent and ethyl alcohol, obtains mixed material.In the present invention
In, the total concentration of the porous carbon materials, conductive agent and binding agent in ethanol is preferably 0.2~1g/L, more preferably 0.5g/
L。
Porous carbon materials are not had special limit by the present invention for described with the mode that conductive agent, binding agent, ethyl alcohol mix
It is fixed, using the technical solution well known to those skilled in the art that can be uniformly mixed raw material.In the present invention, it is described mixed
Conjunction preferably carries out under agitation；The rate of the stirring is preferably 300~500r/min；The time of the stirring is preferably
3~5min.
After completing the mixing, by the coating of obtained mixed material on a current collector, drying obtains carbon electrode to the present invention.
The present invention is for the no special restriction of coating, using the technical solution of coating well known to those skilled in the art.
In the present invention, the load capacity of the porous carbon materials on a current collector is preferably 4~6g/cm2。
After mixed material coating on a current collector, the collector after coating is dried in the present invention, obtains carbon
Electrode.The present invention does not have special restriction for the mode of the drying, using the skill of drying well known to those skilled in the art
Art scheme.In the present invention, the drying is preferably to be dried in vacuo；The vacuum drying vacuum degree is preferably 0.08~
0.12Pa；The vacuum drying temperature is preferably 40~60 DEG C, more preferably 45~55 DEG C；The vacuum drying time is excellent
Elect 8~13h as, more preferably 10~11h.
In order to further illustrate the present invention, with reference to embodiment to the preparation method of porous carbon materials provided by the invention
It is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1:
(1) ground after first straw is dried, then cross the steel sieve of 40 mesh, obtained straw powder is dry at 105 DEG C
12 it is small when；
(2) lye pre-processed using mass concentration as 2% KOH solution as straw, the rice straw powder that step (1) is obtained
End weighs 10g and is mixed with the KOH solution of 100mL；
(3) after the mixture in step (2) is stirred evenly, it is transferred to the stainless steel cauldron of polytetrafluoroethyllining lining
In, carry out oxygenation pretreatment reaction when reaction 4 is small at 120 DEG C；
(4) product obtained in step (3) is cooled down in a cold water bath with the rate of 5 DEG C/min, with the speed of 4000r/min
Rate centrifugation draws black liquor, in an oven freeze-day with constant temperature 12h, removes whole moisture, obtains solid mixture；
(5) solid mixture in step (4) is transferred in corundum boat, be transferred to afterwards in tube furnace, using heating
Rate is kept for a hour be carbonized after rising to 400 DEG C for 2 DEG C/min, then rises to 800 by 5 DEG C/min of heating rate again
Kept for a hour activated after DEG C, carbonization and activation process are protected using nitrogen, airflow rate 800mL/min；
(6) it is cooled to room temperature after reaction, the black powder distilled water and ethyl alcohol of generation alternately wash each 3 times, then
In the whole moisture of 80 DEG C of freeze-day with constant temperature 12h removals, obtain having reached 1357m in the porous carbon materials of black, specific surface area2/
g。
Embodiment 2:
It is 80 in mass ratio by 1 made porous carbon materials of embodiment and acetylene black, polytetrafluoroethylene (PTFE):10:10 ratio into
Row mixing adds in ethyl alcohol and is tuned into even cream, collector is done using nickel foam, and coated in nickel foam, vacuum 0.1Pa is dried at 50 DEG C
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assembling simulation ultracapacitor cell carries out cyclic voltammetric and constant current charge and discharge
Electrical testing.
Experiments have shown that porous carbon materials manufactured in the present embodiment are made after super capacitor, under three electrode tests, than electricity
Appearance has reached 234F/g.
Embodiment 3:
(1) ground after first straw is dried, then cross the steel sieve of 40 mesh, obtained straw powder is dry at 105 DEG C
12 it is small when；
(2) lye pre-processed using mass concentration as 5% KOH solution as straw, the rice straw powder that step (1) is obtained
End weighs 10g and is mixed with the KOH solution of 100mL；
(3) after the mixture in step (2) is stirred evenly, it is transferred to the stainless steel cauldron of polytetrafluoroethyllining lining
In, carry out oxygenation pretreatment reaction when reaction 5 is small at 120 DEG C；
(4) product obtained in step (3) is cooled down in a cold water bath with the rate of 5 DEG C/min, with the speed of 4000r/min
Rate centrifugation draws black liquor, in an oven freeze-day with constant temperature 12h, removes whole moisture, obtains solid mixture；
(5) solid mixture in step (4) is transferred in corundum boat, 400 DEG C is risen to by 2 DEG C/min of heating rate
It is kept for a hour be carbonized afterwards, then is kept for a hour activated after rising to 800 DEG C as 5 DEG C/min using heating rate,
Carbonization and activation process are protected using argon gas, airflow rate 800mL/min；
(6) it is cooled to room temperature after reaction, the black powder distilled water and ethyl alcohol of generation alternately wash each 3 times, then
In the whole moisture of 80 DEG C of freeze-day with constant temperature 12h removals, obtain having reached 1521m in the porous carbon materials of black, specific surface area2/
g。
Embodiment 4:
It is 80 in mass ratio by 3 made porous carbon material of embodiment and super P carbon blacks, Kynoar:10:10 ratio
Example is mixed, and is added in ethyl alcohol and is tuned into even cream, collector is done using nickel foam, coated in nickel foam, vacuum 0.1Pa at 50 DEG C
It is dried overnight, obtains carbon electrode.
Using the KOH of 6mol/L as electrolyte, assembling simulation ultracapacitor cell carries out cyclic voltammetric and constant current charge and discharge
Electrical testing.
Experiments have shown that porous carbon materials manufactured in the present embodiment are made after super capacitor, under three electrode tests, than electricity
Appearance has reached 242F/g.
Embodiment 5:
(1) ground after first straw is dried, then cross the steel sieve of 40 mesh, obtained straw powder is dry at 105 DEG C
12 it is small when；
(2) lye pre-processed using mass concentration as 8% KOH solution as straw, the rice straw powder that step (1) is obtained
End weighs 10g and is mixed with the KOH solution of 100mL；
(3) after the mixture in step (2) is stirred evenly, it is transferred to the stainless steel cauldron of polytetrafluoroethyllining lining
In, carry out oxygenation pretreatment reaction when reaction 6 is small at 120 DEG C；
(4) product obtained in step (3) is cooled down in a cold water bath with the rate of 5 DEG C/min, with the speed of 4000r/min
Rate centrifugation draws black liquor, in an oven freeze-day with constant temperature 12h, removes whole moisture, obtains solid mixture；
(5) solid mixture in step (4) is transferred in corundum boat, be transferred to afterwards in tube furnace, with the speed that heats up
Rate is kept for a hour be carbonized after rising to 400 DEG C for 2 DEG C/min, then is protected after rising to 800 DEG C as 5 DEG C/min using heating rate
Holding a hour is activated, and is carbonized and is activated and is protected using nitrogen, airflow rate 800mL/min；
(6) it is cooled to room temperature after reaction, the black powder distilled water and ethyl alcohol of generation alternately wash each 3 times, then
In the whole moisture of 80 DEG C of freeze-day with constant temperature 12h removals, obtain having reached 1230m in the porous carbon materials of black, specific surface area2/
g。
Embodiment 6:
It is 80 in mass ratio by 5 made porous carbon materials of embodiment and acetylene black, polytetrafluoroethylene (PTFE):10:10 ratio into
Row mixing adds in ethyl alcohol and is tuned into even cream, collector is done using nickel foam, and coated in nickel foam, vacuum 0.1Pa is dried at 50 DEG C
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assembling simulation ultracapacitor cell carries out cyclic voltammetric and constant current charge and discharge
Electrical testing.
Experiments have shown that porous carbon materials manufactured in the present embodiment are made after super capacitor, under three electrode tests, than electricity
Appearance has reached 169F/g.
Embodiment 7:
(1) ground after first straw is dried, then cross the steel sieve of 40 mesh, obtained straw powder is dry at 105 DEG C
12 it is small when；
(2) lye pre-processed using mass concentration as 5% KOH solution as straw, the rice straw powder that step (1) is obtained
End weighs 10g and is mixed with the KOH solution of 100mL；
(3) after the mixture in step (2) is stirred evenly, it is transferred to the stainless steel cauldron of polytetrafluoroethyllining lining
In, carry out oxygenation pretreatment reaction when reaction 4 is small at 120 DEG C；
(4) product obtained in step (3) is cooled down in a cold water bath with the rate of 5 DEG C/min, with the speed of 4000r/min
Rate centrifugation draws black liquor, adds in 1g melamine heating stirrings, in an oven freeze-day with constant temperature 12h, removes whole moisture, consolidate
Body mixture；
(5) solid mixture in step (4) is transferred in corundum boat, be transferred to afterwards in tube furnace, with the speed that heats up
Rate is kept for a hour be carbonized after rising to 400 DEG C for 2 DEG C/min, then rises to 800 DEG C by 5 DEG C/min of heating rate again
It is kept for a hour activated afterwards, is carbonized and activates and protected using nitrogen, airflow rate 800mL/min；
(6) it is cooled to room temperature after reaction, the black powder distilled water and ethyl alcohol of generation alternately wash each 3 times, then
In the whole moisture of 80 DEG C of freeze-day with constant temperature 12h removals, obtain having reached 1357m in the porous carbon materials of black, specific surface area2/
g。
The SEM figures of porous carbon materials manufactured in the present embodiment are as shown in Figure 1, it can be seen from the figure that prepared by the present embodiment
Porous carbon materials have porous structure and larger specific surface area；
The graph of pore diameter distribution of porous carbon materials manufactured in the present embodiment is as shown in Fig. 2, it can be seen from the figure that the present embodiment
To be distributed as 0.5~3nm, distribution is small in the aperture of the porous carbon materials of preparation.
Embodiment 8:
It is 80 in mass ratio by 7 made porous carbon materials of embodiment and super P carbon blacks, polytetrafluoroethylene (PTFE):10:10 ratio
Example is mixed, and is added in ethyl alcohol and is tuned into even cream, collector is done using nickel foam, coated in nickel foam, vacuum 0.1Pa at 50 DEG C
It is dried overnight, obtains carbon electrode.
Using the KOH of 6mol/L as electrolyte, assembling simulation ultracapacitor cell carries out cyclic voltammetric and constant current charge and discharge
Electrical testing.
Experiments have shown that porous carbon materials manufactured in the present embodiment are made after super capacitor, under three electrode tests, than electricity
Appearance has reached 296F/g.
Embodiment 9:
(1) ground after first straw is dried, then cross the steel sieve of 40 mesh, obtained straw powder is dry at 105 DEG C
12 it is small when；
(2) lye pre-processed using mass concentration as 5% KOH solution as straw, the rice straw powder that step (1) is obtained
End weighs 10g and is mixed with the KOH solution of 100mL；
(3) after the mixture in step (2) is stirred evenly, it is transferred to the stainless steel cauldron of polytetrafluoroethyllining lining
In, carry out oxygenation pretreatment reaction when reaction 5 is small at 120 DEG C；
(4) product obtained in step (3) is cooled down in a cold water bath with the rate of 5 DEG C/min, with the speed of 4000r/min
Rate centrifugation draws black liquor, adds in 2g melamine heating stirrings, in an oven freeze-day with constant temperature 12h, removes whole moisture, consolidate
Body mixture；
(5) solid mixture in step (4) is transferred in corundum boat, be transferred to afterwards in tube furnace, using heating
Rate is kept for a hour be carbonized after rising to 400 DEG C for 2 DEG C/min, then after rising to 800 DEG C as 5 DEG C/min using heating rate
It is kept for a hour activated, is carbonized and activates and protected using nitrogen, airflow rate 800mL/min；
(6) it is cooled to room temperature after reaction, the black powder distilled water and ethyl alcohol of generation alternately wash each 3 times, then
In the whole moisture of 80 DEG C of freeze-day with constant temperature 12h removals, obtain having reached 1357m in the porous carbon materials of black, specific surface area2/
g。
The SEM figures of porous carbon materials manufactured in the present embodiment are as shown in figure 3, it can be seen from the figure that prepared by the present embodiment
Porous carbon materials have porous structure and larger specific surface area；
The graph of pore diameter distribution of porous carbon materials manufactured in the present embodiment is as shown in figure 4, it can be seen from the figure that the present embodiment
To be distributed as 0.5~3nm, distribution is small in the aperture of the porous carbon materials of preparation.
Embodiment 10:
It is 80 in mass ratio by 9 made porous carbon materials of embodiment and acetylene black, Kynoar:10:10 ratio into
Row mixing adds in ethyl alcohol and is tuned into even cream, collector is done using nickel foam, and coated in nickel foam, vacuum 0.1Pa is dried at 50 DEG C
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assembling simulation ultracapacitor cell carries out cyclic voltammetric and constant current charge and discharge
Electrical testing.
The cyclic voltammetry curve and constant current charge-discharge curve of carbon electrode manufactured in the present embodiment are distinguished as shown in Figure 5 and Figure 6,
It can be seen from the figure that carbon electrode provided in this embodiment has good chemical property.
Experiments have shown that porous carbon materials manufactured in the present embodiment are made after super capacitor, under three electrode tests, than electricity
Appearance has reached 337F/g.
Embodiment 11:
(1) ground after first straw is dried, then cross the steel sieve of 40 mesh, obtained straw powder is dry at 105 DEG C
12 it is small when；
(2) lye pre-processed using mass concentration as 5% KOH solution as straw, the rice straw powder that step (1) is obtained
End weighs 10g and is mixed with the KOH solution of 100mL；
(3) after the mixture in step (2) is stirred evenly, it is transferred to the stainless steel cauldron of polytetrafluoroethyllining lining
In, carry out oxygenation pretreatment reaction when reaction 6 is small at 120 DEG C；
(4) product obtained in step (3) is cooled down in a cold water bath with the rate of 5 DEG C/min, with the speed of 4000r/min
Rate centrifugation draws black liquor, adds in 4g melamine heating stirrings, in an oven freeze-day with constant temperature 12h, removes whole moisture, consolidate
Body mixture；
(5) solid mixture in step (4) is transferred in corundum boat, be transferred to afterwards in tube furnace, using heating
Rate is kept for a hour be carbonized after rising to 400 DEG C for 2 DEG C/min, then after rising to 800 DEG C as 5 DEG C/min using heating rate
It is kept for a hour activated, is carbonized and activates and protected using argon gas, airflow rate 800mL/min；
(6) it is cooled to room temperature after reaction, the black powder distilled water and ethyl alcohol of generation alternately wash each 3 times, then
In the whole moisture of 80 DEG C of freeze-day with constant temperature 12h removals, obtain having reached 1357m in the porous carbon materials of black, specific surface area2/
g。
The SEM figures of porous carbon materials manufactured in the present embodiment are as shown in fig. 7, it can be seen from the figure that prepared by the present embodiment
Porous carbon materials have porous structure and larger specific surface area；
The graph of pore diameter distribution of porous carbon materials manufactured in the present embodiment is as shown in figure 8, it can be seen from the figure that the present embodiment
To be distributed as 0.5~3nm, distribution is small in the aperture of the porous carbon materials of preparation.
Embodiment 12:
It is 80 in mass ratio by 11 made porous carbon materials of embodiment and acetylene black, polytetrafluoroethylene (PTFE):10:10 ratio into
Row mixing adds in ethyl alcohol and is tuned into even cream, collector is done using nickel foam, and coated in nickel foam, vacuum 0.1Pa is dried at 50 DEG C
Overnight, carbon electrode is obtained.
Using the KOH of 6mol/L as electrolyte, assembling simulation ultracapacitor cell carries out cyclic voltammetric and constant current charge and discharge
Electrical testing.
Experiments have shown that porous carbon materials manufactured in the present embodiment are made after super capacitor, under three electrode tests, than electricity
Appearance has reached 232F/g.
As can be seen from the above embodiments, the porous carbon materials that prepared by preparation method provided by the invention have high-ratio surface
Product, the carbon electrode of preparation are used for having good chemical property during super capacitor.
The above is only the preferred embodiment of the present invention, not makees limitation in any form to the present invention.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of preparation method of porous carbon materials, comprises the following steps：
(1) black liquid is pre-processed, obtains solid mixture, the black liquid contains for what alkali paper-making generated
The waste liquid of KOH；The black liquid is mixed before pretreatment with melamine, and the quality of the melamine is black liquid matter
The 0.2~5% of amount；
(2) solid mixture that the step (1) obtains is carbonized, obtains carbon material；
(3) carbon material that the step (2) obtains is activated, obtains porous carbon materials.
2. preparation method according to claim 1, which is characterized in that carbonization is in inert gas shielding in the step (2)
Lower progress.
3. preparation method according to claim 1 or 2, which is characterized in that the temperature of the carbonization is 350~450 DEG C, carbon
The time of change is 0.5~1.5h.
4. preparation method according to claim 1, which is characterized in that activation is in inert gas shielding in the step (3)
Lower progress.
5. the preparation method according to claim 1 or 4, which is characterized in that the temperature of the activation is 600~900 DEG C, living
The time of change is 0.5~1.5h.
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| CN106744793B (en) * | 2016-12-01 | 2019-04-05 | 中国林业科学研究院林产化学工业研究所 | A kind of alkali lignin based super capacitor porous carbon material and its preparation method and application |
| CN108630453B (en) * | 2017-03-16 | 2020-09-29 | 中国海洋大学 | Method for preparing graphene-like carbon nanosheet material by one-step method and application of graphene-like carbon nanosheet material |
| CN107910200A (en) * | 2017-10-23 | 2018-04-13 | 河南师范大学 | A kind of preparation method of multi-stage porous nitrogen oxygen doping carbon supercapacitor electrode material |
| CN107934959A (en) * | 2017-12-05 | 2018-04-20 | 中国林业科学研究院林产化学工业研究所 | A kind of lignin-base grading-hole Carbon Materials and its preparation method and application |
| CN107840334A (en) * | 2017-12-19 | 2018-03-27 | 中国石油大学(华东) | A kind of atomic hole porous carbon materials and preparation method thereof |
| CN107827108A (en) * | 2017-12-19 | 2018-03-23 | 中国石油大学(华东) | A kind of pole micro-pore carbon material and preparation method thereof |
| CN109485029B (en) | 2018-11-19 | 2020-07-28 | 华南理工大学 | Lignin porous carbon nanosheet, preparation method thereof and application thereof in supercapacitor electrode material |
| CN109728315A (en) * | 2018-12-27 | 2019-05-07 | 华北电力大学 | Modified carbonized celulose cardboard electrode material and microbiological fuel cell |
| CN109592665B (en) * | 2019-01-21 | 2022-05-17 | 兖矿集团有限公司 | Preparation method of nano-porous carbon material |
| CN110483050A (en) * | 2019-09-25 | 2019-11-22 | 华东理工大学 | A kind of photocuring 3D printing step porous carbon materials and preparation method thereof |
| CN113816374B (en) * | 2021-09-29 | 2022-12-27 | 海南金海浆纸业有限公司 | Method for preparing high-adsorption-performance activated carbon by using pulping black liquor |
| CN113998682B (en) * | 2021-11-10 | 2023-05-30 | 青岛农业大学 | Green, simple and convenient lignin-based foam carbon and preparation method and application thereof |
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