CN108275676A - A method of preparing nitrogen-doped graphene - Google Patents
A method of preparing nitrogen-doped graphene Download PDFInfo
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- CN108275676A CN108275676A CN201810307991.6A CN201810307991A CN108275676A CN 108275676 A CN108275676 A CN 108275676A CN 201810307991 A CN201810307991 A CN 201810307991A CN 108275676 A CN108275676 A CN 108275676A
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Abstract
A method of nitrogen-doped graphene is prepared, including：Step 1：5g graphite, 1g sodium nitrate are weighed, 2 grams of potassium nitrate and 2 grams of sodium bicarbonates are placed in the beaker of 1000mL, the 150mL concentrated sulfuric acids are slowly added into beaker, beaker is placed in ice-water bath, magnetic agitation 1h;Step 2：Weigh 15g potassium permanganate and 2 grams of sodium permanganates, be slowly added in beaker and be stirred continuously, keep in beaker mixture temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours.
Description
Technical field
The present invention relates to a kind of methods preparing nitrogen-doped graphene.
Background technology
The method flow in the prior art for preparing nitrogen-doped graphene is complicated, low precision, not environmentally.
Invention content
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2 grams of sodium bicarbonates are placed in the beaker of 1000mL, to beaker
In be slowly added to the 150mL concentrated sulfuric acids, beaker is placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Inventive point is：1）Complete reaction process；2）Material used；3）Concrete component.
Specific implementation mode
Embodiment 1
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2 grams of sodium bicarbonates are placed in the beaker of 1000mL, to beaker
In be slowly added to the 150mL concentrated sulfuric acids, beaker is placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 2
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.2 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 3
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.3 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 4
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.4 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 5
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.5 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 6
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.6 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 7
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.7 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 8
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.8 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 9
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2.9 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 10
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 3 grams of sodium bicarbonates are placed in the beaker of 1000mL, to beaker
In be slowly added to the 150mL concentrated sulfuric acids, beaker is placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Embodiment 11
A method of nitrogen-doped graphene is prepared, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 3.1 grams of sodium bicarbonates are placed in the beaker of 1000mL, to burning
The 150mL concentrated sulfuric acids are slowly added in cup, beaker are placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
The nitrogen-doped graphene of the present invention can be applied to super capacitor.
Claims (2)
1. a kind of method preparing nitrogen-doped graphene, including：
Step 1：5g graphite is weighed, 1g sodium nitrate, 2 grams of potassium nitrate and 2 grams of sodium bicarbonates are placed in the beaker of 1000mL, to beaker
In be slowly added to the 150mL concentrated sulfuric acids, beaker is placed in ice-water bath, magnetic agitation 1h;
Step 2：15g potassium permanganate and 2 grams of sodium permanganates are weighed, is slowly added in beaker and is stirred continuously, keep mixing in beaker
Close object temperature 30 DEG C hereinafter, beaker to be placed in room temperature later under be stirred continuously for 24 hours;
Step 3：Beaker is placed in ice-water bath, 300mL deionized waters are slowly added to and is stirred continuously, mixture in beaker is kept
Temperature is at 98 DEG C hereinafter, being then slowly added into the aqueous hydrogen peroxide solution that 30mL mass fractions are 30% and being stirred continuously;
Step 4：Mixed solution is packed into centrifuge tube, 30min is centrifuged at 8000rpm, supernatant liquid is removed, sediment is taken
Go out, the aqueous hydrochloric acid solution for being 10% with volume fraction wash and centrifuged 6 times, sediment is taken out to be placed in bag filter carries out by a definite date 3
The dialysis in week obtains graphite oxide suspension to remove salt ion and acid ion completely;
Step 5：Graphite oxide suspension is scattered in deionized water, configuration quality score is the suspension of 1mg/mL, to it
Ultrasonic disperse processing is carried out, ultrasonic time 1h centrifuges 30min and removes unstripped graphite oxide at 3,000 rpm, final to obtain
To graphene oxide aqueous dispersions；
Step 6：Using graphene oxide aqueous dispersions made from step 5, configuration concentration is the graphene oxide water of 0.3mg/mL
Dispersion liquid takes 500mL graphene oxide aqueous dispersions to be placed in three-neck flask；
Step 7：Three-neck flask is fixed on iron stand, middle port and side eck are covered tightly with glass stopper, pass through the other side
It is molten that the hydrazine that the ammonium hydroxide that 1mL mass fractions are 28wt.% and 80 μ L mass fractions are 80wt.% is added into three-neck flask for eck
Then liquid also covers tightly this side port with glass stopper, and carry out abundant magnetic agitation；
Step 8：Spiral coil cooling tube is placed on the interstitial hole of three-neck flask, is opened cooling water and is filled coiled pipe and keep water outlet
Flow be in small thread shape, adjust iron stand geometrical clamp position, three-neck flask is placed in 95 DEG C of oil bath and reacts 1h,
Period keeps sufficient magnetic agitation, after completion of the reaction takes out three-neck flask from oil bath；
Step 9：After cooled to room temperature, the black suspension in bottle is filtered to remove in draught cupboard after three-neck flask
It removes to swim in apparent large stretch of carbon-coating on liquid level, redox graphene is obtained after then suspension is filtered and dried；
Step 10：Using redox graphene made from step 9 as raw material, configuration concentration is the redox graphene of 5mg/mL
Aqueous solution 40mL is placed in the plastic bottle that capacity is 60mL, the potassium hydroxide solution of point a concentration of 6mol/L of addition 3mL, abundant magnetic
Power seals placement 12h after stirring 2h under room temperature；
Step 11：Mixed liquor made from step 10 is subjected to freeze-drying 72h at -55 DEG C；
Step 12：Sample after freeze-drying is placed in tube furnace, is heat-treated under argon gas atmosphere protection：First to pipe
Formula stove carries out vacuum pumping, and setting heating rate is 20 DEG C/min, and target temperature is 800 DEG C, soaking time 30min, argon
Throughput is 400sccm, and operating air pressure 100Pa cools to room temperature with the furnace after reaction；
Step 13：The product of step 12 is washed 2 times with the aqueous hydrochloric acid solution that volume fraction is 10%, then is washed with deionized
It is about 7 to pH value, product is freeze-dried, obtains the redox graphene of activation of potassium hydroxide；
Step 14：The redox graphene of activation of potassium hydroxide made from step 13 is placed in tube furnace, to tube furnace into
Row vacuumizes, and temperature control program is then arranged：Heating rate is 20 DEG C/min, and target temperature is respectively 800 DEG C, and soaking time is
1h, later with stove natural cooling；
Step 15：It is heating up and is being passed through ammonia, flow 100sccm in insulating process, the flow for being passed through argon gas is 20sccm, work
It is 1000Pa to make air pressure, is passed through ammonia in temperature-fall period stopping, continuing to be passed through argon gas, N doping stone is made in flow 400sccm
Black alkene.
2. the nitrogen-doped graphene of the present invention can be applied to super capacitor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346338A (en) * | 2018-11-16 | 2019-02-15 | 郑州轻工业学院 | A kind of fast room-temperature preparation method of nitrogen-doped graphene |
| CN109607524A (en) * | 2019-01-31 | 2019-04-12 | 清华大学深圳研究生院 | Porous nitrogen-doped graphene material, preparation method and lithium ion battery |
| CN110155998A (en) * | 2019-05-13 | 2019-08-23 | 东南大学 | A kind of ribbon nitrogen-doped graphene and its preparation method and application |
| CN113871645A (en) * | 2021-09-29 | 2021-12-31 | 北京化工大学 | Preparation method of uniformly-loaded carbon nanotube platinum-loaded electrocatalyst |
-
2018
- 2018-04-08 CN CN201810307991.6A patent/CN108275676A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109346338A (en) * | 2018-11-16 | 2019-02-15 | 郑州轻工业学院 | A kind of fast room-temperature preparation method of nitrogen-doped graphene |
| CN109607524A (en) * | 2019-01-31 | 2019-04-12 | 清华大学深圳研究生院 | Porous nitrogen-doped graphene material, preparation method and lithium ion battery |
| CN110155998A (en) * | 2019-05-13 | 2019-08-23 | 东南大学 | A kind of ribbon nitrogen-doped graphene and its preparation method and application |
| CN110155998B (en) * | 2019-05-13 | 2023-02-21 | 东南大学 | Strip-shaped nitrogen-doped graphene and preparation method and application thereof |
| CN113871645A (en) * | 2021-09-29 | 2021-12-31 | 北京化工大学 | Preparation method of uniformly-loaded carbon nanotube platinum-loaded electrocatalyst |
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