CN105097298A - Method for preparing graphene hydrogel electrode by graphene oxide solution - Google Patents
Method for preparing graphene hydrogel electrode by graphene oxide solution Download PDFInfo
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- CN105097298A CN105097298A CN201510278333.5A CN201510278333A CN105097298A CN 105097298 A CN105097298 A CN 105097298A CN 201510278333 A CN201510278333 A CN 201510278333A CN 105097298 A CN105097298 A CN 105097298A
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Abstract
A method for preparing a graphene hydrogel electrode by a graphene oxide solution relates to the preparation of hydrogel, and solves the problem of complicated methods in preparing supercapacitor graphene electrodes in the prior art; a preparation method for the graphene electrode with mild reaction conditions, short process time, simple operation, lower energy consumption and capability of controlling shapes of the electrodes is provided. The method comprises steps of: preparing a graphene oxide dispersion liquid by adding 1-4L of deionized water into each 1 g of graphene oxide powder, stirring for 6-12 hours at 50-150 rpm, preparing a mixed liquid by adding 0.5-4 g of sodium sulphide or 0.5-4 g of ascorbic acid used as a reducing agent into each 1 g of graphene oxide powder; stirring the prepared mixed liquid for 1-10 min, standing for 0.5-36 hours, then pouring the mixed liquid into sample bottles with corresponding shapes with the shapes of electrodes, sealing the bottles, heating at the temperature of 80-95 DEG C for 3-10 hours; and taking black solid out of the sample bottles, soaking the black solid by deionized water for at least 20 hours to obtain the graphene hydrogel electrode.
Description
Technical field
The present invention relates to the hydrogel preparation of stereochemical structure, is that a kind of graphene oxide water solution one step that utilizes is reduced and forms the preparation method of Graphene hydrogel.Be adapted at using as electrode in ultracapacitor.
Background technology
The two dimensional surface network structure that Graphene is made up of carbon atom, has specific area large, excellent thermal conductivity, and mechanical strength is large, electric transmission rate high.Be that various new material that raw material is prepared is compared with traditional material and had more performance advantage and the scope of application widely with Graphene.The three-dimensional self supporting structure of Graphene hydrogel makes it have broad application prospects in ultracapacitor field.
Present stage, using method utilizes dry graphene oxide powder at 800 ~ 900 DEG C of high temperature and be filled with thermal expansion in the environment of protective gas to obtain graphene powder, and itself and binding agent and other electric conducting material are mixed and made into electrode of super capacitor.The high temperature of more than 800 DEG C and the environment of isolated air require higher to consersion unit, and reduce the reduction rate of graphene oxide, namely the consumption simultaneously turn increasing electric energy and protective gas increase cost.And the process mixed with binding agent and electric conducting material not only makes whole manufacturing process link more, consuming time more, operate more complicated, further increase total cost again simultaneously.
Summary of the invention
Technical problem to be solved by this invention improves the complicated approach that prior art prepares ultracapacitor Graphene electrodes, and provide a kind of reaction condition gentle, process time is short, and energy consumption simple to operate is lower, the controllable Graphene electrodes preparation method of electrode shape.The temperature that this method needs is low, and decrease energy resource consumption, course of reaction only has a step, decreases reaction required time.
The technical scheme solving its technical problem is to provide a kind of method utilizing graphene oxide solution to prepare Graphene hydrogel electrode, and the step of this preparation method comprises:
Step one, takes graphite powder, by every 1g graphite powder correspondence 20 ~ 30mL98% concentrated sulfuric acid and 3 ~ 8g potassium permanganate proportioning feeding;
Step 2,98% concentrated sulfuric acid of ratio corresponding in step one is put into glass container and is placed in ice bath environment, open and stir, until temperature is down to 10 ~ 0 DEG C, the graphite powder of ratio corresponding in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 2 ~ 4h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3, the potassium permanganate of corresponding ratio is added in the mixed liquor of step 2, continue to stir 2 ~ 4h with 100rpm, the glass container filling mixed liquor is placed in heating environment, after equitemperature rises to room temperature, adds 140mL deionized water with every 1g graphite powder, and continue to stir with 100rpm, temperature controls at 90 ~ 95 DEG C, stops heating afterwards, now obtained new mixed liquor;
Step 4, in the new mixed liquor that step 3 obtains, adds the hydrogen peroxide of 10mL30% with every 1g graphite powder, stir 10min with 100rpm, mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 1 ~ 6% hydrochloric acid, 5 ~ 30min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 1 ~ 5mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid that concentration is 1 ~ 6% is added in secondary sediment, 5 ~ 30min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 1 ~ 5mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid that concentration is 1 ~ 6% is added in the sediment of third time, 5 ~ 30min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 1 ~ 5mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical, the concentration of hydrochloric acid of above-mentioned use be 1 ~ 6% consumption be 60 ~ 100mL;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 60mL with every 1g graphite powder and centrifugal, retain sediment and again add 60mL deionized water with every 1g graphite powder, 10min is centrifugal after stirring 5 ~ 20min, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 60mL deionized water with every 1g graphite powder and stirs 5 ~ 20min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, the graphene oxide powder that step 7 is obtained, add 0.25 ~ 1L deionized water by every 1g and be mixed with graphene oxide dispersion, stir 6 ~ 12h with 50 ~ 150rpm, add 0.5 ~ 4g vulcanized sodium with every 1g graphene oxide powder or 0.5 ~ 4g ascorbic acid becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, after stirring 1 ~ 10min with 50 ~ 150rpm, after leaving standstill 0.5 ~ 36h, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 80 ~ 95 DEG C, and heating time is 3 ~ 10h; The black solid deionized water taken out in sample bottle soaks, and the time of immersion is not less than 20h, obtains Graphene hydrogel electrode.
Beneficial effect of the present invention:
The present invention obtains finely dispersed graphene oxide dispersion by the stirring that adds water of graphene oxide powder, reduce the ambient temperature of reduction reaction by adding reducing agent in the process of reduction reaction, many spaces stereochemical structure that directly can be used as electrode and the reduction both having completed graphene oxide in same process has been got back, and the shape of Graphene hydrogel electrode can be controlled by the shape controlling container, simplify the step of conventional method, shorten the time of whole course of reaction, utilize Graphene bigger serface, the characteristics such as high electron mobility, its hydrogel is with a wide range of applications in energy storage field.
Accompanying drawing explanation
The Graphene hydrogel photo that Fig. 1 utilizes vulcanized sodium to obtain as reducing agent;
The Graphene hydrogel photo that Fig. 2 utilizes ascorbic acid to obtain as reducing agent;
The Graphene hydrogel SEM photo that Fig. 3 utilizes vulcanized sodium to obtain as reducing agent;
The Graphene hydrogel SEM photo that Fig. 4 utilizes ascorbic acid to obtain as reducing agent.
Embodiment
Embodiment one
Utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the method comprises:
Step one, takes 5g graphite powder, the 100mL98% concentrated sulfuric acid and 15g potassium permanganate;
Step 2,98% concentrated sulfuric acid in step one put into glass container and is placed in ice bath environment, opening and stir, until temperature is down to 0 DEG C, graphite powder in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 2h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3,15g potassium permanganate is added in the mixed liquor of step 2, continue to stir 2h with 100rpm, to the glass container of mixed liquor be filled as in heating environment, equitemperature adds 700mL deionized water after rising to room temperature, and continues to stir with 100rpm, and temperature controls at 90 DEG C, stop heating afterwards, now obtained new mixed liquor;
Step 4, adds the hydrogen peroxide of 50mL30% in the new mixed liquor that step 3 obtains, and stir with 100rpm, mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 1% hydrochloric acid 60mL, 5min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 1mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid 60mL that concentration is 1% is added in secondary sediment, 5min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 1mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid 60mL that concentration is 1% is added in the sediment of third time, 5min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 1mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 300mL and centrifugal, retain sediment and again add 300mL deionized water, centrifugal after stirring 5min with 100rpm, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 300mL deionized water and stirs 5min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, gets the graphene oxide powder 5g obtained in step 7, joins in 5L deionized water and be mixed with graphene oxide dispersion, and stir 6h with 50rpm, adding 2.5g vulcanized sodium becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, after stirring 1min with 50rpm, leave standstill 0.5h, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 80 DEG C, and heating time is 3h; The black solid deionized water taken out in sample bottle soaks 20h, to remove impurity, obtains Graphene hydrogel electrode.Fig. 1 is final obtained Graphene hydrogel electrode, and Fig. 3 is electrode stereochemical structure TEM photo.
Embodiment two
Utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the method comprises:
Step one, takes 5g graphite powder, the 150mL98% concentrated sulfuric acid and 40g potassium permanganate;
Step 2,98% concentrated sulfuric acid in step one put into glass container and is placed in ice bath environment, opening and stir, until temperature is down to 10 DEG C, graphite powder in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 4h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3,40g potassium permanganate is added in the mixed liquor of step 2, continue to stir 4h with 100rpm, to the glass container of mixed liquor be filled as in heating environment, equitemperature adds 700mL deionized water after rising to room temperature, and continues to stir with 100rpm, and temperature controls at 95 DEG C, stop heating afterwards, now obtained new mixed liquor.
Step 4, in the new mixed liquor that step 3 obtains, add the hydrogen peroxide of 50mL30%, new mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 6% hydrochloric acid 100mL, 30min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 5mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid 100mL that concentration is 6% is added in secondary sediment, 30min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 5mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid 100mL that concentration is 6% is added in the sediment of third time, 30min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 5mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 300mL and centrifugal, take out sediment and again add 300mL deionized water, centrifugal after stirring 20min with 100rpm, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 300mL deionized water and stirs 20min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, gets the graphene oxide powder 5g obtained in step 7, and add 1.25L deionized water preparation composition graphene oxide dispersion, stir 12h with 150rpm, adding 20g vulcanized sodium becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, leave standstill 36h after stirring 10min with 150rpm, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 95 DEG C, and the time is 10h; The black solid deionized water taken out in sample bottle soaks 40h, to remove impurity, obtains Graphene hydrogel electrode.
Embodiment three
Utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the method comprises:
Step one, takes 5g graphite powder, the 100mL98% concentrated sulfuric acid and 15g potassium permanganate;
Step 2,98% concentrated sulfuric acid in step one put into glass container and is placed in ice bath environment, opening and stir, until temperature is down to 0 DEG C, graphite powder in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 2h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3,15g potassium permanganate is added in the mixed liquor of step 2, continue to stir 2h with 100rpm, to the glass container of mixed liquor be filled as in heating environment, equitemperature adds 700mL deionized water after rising to room temperature, and continues to stir with 100rpm, and temperature controls at 90 DEG C, stop heating mixed liquor afterwards, now obtained new mixed liquor;
Step 4, in the new mixed liquor that step 3 obtains, add the hydrogen peroxide of 50mL30%, new mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 3% hydrochloric acid 60mL, 15min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 3mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid 60mL that concentration is 3% is added in secondary sediment, 15min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 3mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid 60mL that concentration is 3% is added in the sediment of third time, 15min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 3mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 300mL and centrifugal, take out sediment and again add 300mL deionized water, centrifugal after stirring 5min with 100rpm, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 300mL deionized water and stirs 5min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, gets the graphene oxide powder 5g obtained in step 7, and join 2L deionized water preparation composition graphene oxide and to fall apart liquid, stir 6h with 50rpm, adding 2.5g ascorbic acid becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, leave standstill 0.5h after stirring 1min with 50rpm, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 80 DEG C, and the time is 3h; The black solid deionized water taken out in sample bottle soaks 20h, to remove impurity, obtains Graphene hydrogel electrode.Fig. 2 is final obtained Graphene hydrogel electrode, and Fig. 4 is electrode stereochemical structure TEM photo.
Embodiment four
Utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the method comprises:
Step one, takes 5g graphite powder, the 150mL98% concentrated sulfuric acid and 40g potassium permanganate;
Step 2,98% concentrated sulfuric acid in step one put into glass container and is placed in ice bath environment, opening and stir, until temperature is down to 10 DEG C, graphite powder in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 4h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3,40g potassium permanganate is added in the mixed liquor of step 2, continue to stir 4h with 100rpm, to the glass container of mixed liquor be filled as in heating environment, equitemperature adds 700mL deionized water after rising to room temperature, and continues to stir with 100rpm, and temperature controls at 95 DEG C, stop heating afterwards, now obtained new mixed liquor;
Step 4, in the new mixed liquor that step 3 obtains, add the hydrogen peroxide of 50mL30%, new mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is that 2% hydrochloric acid 100mL stirs 10min with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 2mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid 100mL that concentration is 2% is added in secondary sediment, 10min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 2mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid 100mL that concentration is 2% is added in the sediment of third time, 10min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 2mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 300mL and centrifugal, take out sediment and again add 300mL deionized water, centrifugal after stirring 20min with 100rpm, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 300mL deionized water and stirs 20min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, gets the graphene oxide powder 5g obtained in step 7, joins 2L deionized water and be mixed with graphene oxide dispersion, and stir 12h with 150rpm, adding 4g ascorbic acid becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, leave standstill 36h after stirring 10min with 150rpm, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 95 DEG C, and the time is 10h; The black solid deionized water taken out in sample bottle soaks 40h, to remove impurity, obtains Graphene hydrogel electrode.
Embodiment five
Utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the method comprises:
Step one, takes 5g graphite powder, the 125mL98% concentrated sulfuric acid and 25g potassium permanganate;
Step 2,98% concentrated sulfuric acid in step one put into glass container and is placed in ice bath environment, opening and stir, until temperature is down to 5 DEG C, graphite powder in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 3h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3,25g potassium permanganate is added in the mixed liquor of step 2, continue to stir 3h with 100rpm, to the glass container of mixed liquor be filled as in heating environment, equitemperature adds 700mL deionized water after rising to room temperature, and continues to stir with 100rpm, and temperature controls at 93 DEG C, stop heating afterwards, now obtained new mixed liquor.
Step 4, in the new mixed liquor that step 3 obtains, add the hydrogen peroxide of 50mL30%, new mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 4% hydrochloric acid 75mL, 20min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 4mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid 75mL that concentration is 4% is added in secondary sediment, 20min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 4mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid 75mL that concentration is 4% is added in the sediment of third time, 20min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 4mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 300mL and centrifugal, take out sediment and again add 300mL deionized water, centrifugal after stirring 10min with 100rpm, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 300mL deionized water and stirs 10min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, gets the graphene oxide powder 5g obtained in step 7, joins 2.5L deionized water and be mixed with graphene oxide dispersion, and stir 9h with 100rpm, adding 10g vulcanized sodium becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, leave standstill 20h after stirring 5min with 100rpm, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 90 DEG C, and the time is 6h; The black solid deionized water taken out in sample bottle soaks 24h, to remove impurity, obtains Graphene hydrogel electrode.
Embodiment six
Utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the method comprises:
Step one, takes 5g graphite powder, the 110mL98% concentrated sulfuric acid and 20g potassium permanganate;
Step 2,98% concentrated sulfuric acid in step one put into glass container and is placed in ice bath environment, opening and stir, until temperature is down to 3 DEG C, graphite powder in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 2.5h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3,20g potassium permanganate is added in the mixed liquor of step 2, continue to stir 2.5h with 100rpm, to the glass container of mixed liquor be filled as in heating environment, equitemperature adds 700mL deionized water after rising to room temperature, and continues to stir with 100rpm, and temperature controls at 93 DEG C, stop heating mixed liquor afterwards, now obtained new mixed liquor;
Step 4, in the new mixed liquor that step 3 obtains, add the hydrogen peroxide of 50mL30%, new mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 6% hydrochloric acid 80mL, 5min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 1mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid 80mL that concentration is 1% is added in secondary sediment, 5min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 1mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid 80mL that concentration is 6% is added in the sediment of third time, 5min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 1mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 300mL and centrifugal, take out sediment and again add 300mL deionized water, centrifugal after stirring 12min with 100rpm, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 300mL deionized water and stirs 12min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, gets the graphene oxide powder 5g obtained in step 7, joins 4.5L deionized water and be mixed with graphene oxide dispersion, and stir 7.5h with 120rpm, adding 7.5g vulcanized sodium becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, leave standstill 10h after stirring 3min with 120rpm, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 85 DEG C, and the time is 4.5h; The black solid deionized water taken out in sample bottle soaks 21h, to remove impurity, obtains Graphene hydrogel electrode.
Embodiment seven
Utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the method comprises:
Step one, takes 5g graphite powder, the 110mL98% concentrated sulfuric acid and 20g potassium permanganate;
Step 2,98% concentrated sulfuric acid in step one put into glass container and is placed in ice bath environment, opening and stir, until temperature is down to 3 DEG C, graphite powder in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 2.5h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3,20g potassium permanganate is added in the mixed liquor of step 2, continue to stir 2.5h with 100rpm, to the glass container of mixed liquor be filled as in heating environment, equitemperature adds 700mL deionized water after rising to room temperature, and continues to stir with 100rpm, and temperature controls at 93 DEG C, stop heating mixed liquor afterwards, now obtained new mixed liquor.
Step 4, in the new mixed liquor that step 3 obtains, add the hydrogen peroxide of 50mL30%, new mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 1% hydrochloric acid 80mL, 5min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 5mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid 80mL that concentration is 6% is added in secondary sediment, 5min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 2mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid 80mL that concentration is 5% is added in the sediment of third time, 5min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 5mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 300mL and centrifugal, take out sediment and again add 300mL deionized water, centrifugal after stirring 17min with 100rpm, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 300mL deionized water and stirs 17min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
Step 8, gets the graphene oxide powder 5g obtained in step 7, joins 3.5L deionized water and be mixed with graphene oxide dispersion, and stir 10h with 75rpm, adding 15g ascorbic acid becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, leave standstill 30h after stirring 9min with 75rpm, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 93 DEG C, and the time is 9h; The black solid deionized water taken out in sample bottle soaks 23h, to remove impurity, obtains Graphene hydrogel electrode.
Claims (1)
1. utilize graphene oxide solution to prepare a method for Graphene hydrogel electrode, the step of this preparation method comprises:
Step one, takes graphite powder, by every 1g graphite powder correspondence 20 ~ 30mL98% concentrated sulfuric acid and 3 ~ 8g potassium permanganate proportioning feeding;
Step 2,98% concentrated sulfuric acid of ratio corresponding in step one is put into glass container and is placed in ice bath environment, open and stir, until temperature is down to 10 ~ 0 DEG C, the graphite powder of ratio corresponding in step one is added in 98% concentrated sulfuric acid in glass container, stir with 100rpm the mixed liquor that 2 ~ 4h obtains graphite powder and 98% concentrated sulfuric acid;
Step 3, the potassium permanganate of corresponding ratio is added in the mixed liquor of step 2, continue to stir 2 ~ 4h with 100rpm, the glass container filling mixed liquor is placed in heating environment, after equitemperature rises to room temperature, adds 140mL deionized water with every 1g graphite powder, and continue to stir with 100rpm, temperature controls at 90 ~ 95 DEG C, stops heating afterwards, now obtained new mixed liquor;
Step 4, in the new mixed liquor that step 3 obtains, adds the hydrogen peroxide of 10mL30% with every 1g graphite powder, stir 10min with 100rpm, mixed liquor produces a large amount of bubble and becomes flavous mixed liquor;
Step 5, golden yellow mixed liquor step 4 obtained is placed in centrifugal bottle, put into centrifuge, it is centrifugal to carry out first time, after centrifugal, supernatant and for the first time sediment is for the first time divided in centrifugal bottle, take out primary supernatant, in first time sediment, add concentration is 1 ~ 6% hydrochloric acid, 5 ~ 30min is stirred with 100rpm, carry out second time centrifugal, now, second time supernatant and second time sediment is divided in centrifugal bottle, supernatant after centrifugal for second time is taken out, instillation 1 ~ 5mol/L barium chloride solution, adularescent barium sulfate produces, illustrating in secondary supernatant has sulfate radical to exist,
The watery hydrochloric acid that concentration is 1 ~ 6% is added in secondary sediment, 5 ~ 30min is stirred with 100rpm, it is centrifugal to carry out third time, after centrifugal, be divided into supernatant and for the third time sediment for the third time in centrifugal bottle, the supernatant after centrifugal for third time taken out, instills 1 ~ 5mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of third time and has sulfate radical to exist;
The watery hydrochloric acid that concentration is 1 ~ 6% is added in the sediment of third time, 5 ~ 30min is stirred with 100rpm, carry out the 4th time centrifugal, after centrifugal, be divided into the 4th supernatant and the 4th precipitation in centrifugal bottle, the supernatant after centrifugal by the 4th time is poured in container, instillation 1 ~ 5mol/L barium chloride solution, adularescent barium sulfate produces, and illustrates in the supernatant of the 4th time and has sulfate radical to exist;
Repeat said process, until do not have white barium sulfate to produce, now sediment is the sediment not having sulfate radical, the concentration of hydrochloric acid of above-mentioned use be 1 ~ 6% consumption be 60 ~ 100mL;
Step 6, by collect in step 5 do not have the sediment of sulfate radical to add the deionized water of 60mL with every 1g graphite powder and centrifugal, retain sediment and again add 60mL deionized water with every 1g graphite powder, 10min is centrifugal after stirring 5 ~ 20min, repeat said process, until the supernatant after centrifugal is neutral, collect neutral sediment now;
Step 7, the neutral sediment obtained in step 6 adds 60mL deionized water with every 1g graphite powder and stirs 5 ~ 20min with 100rpm, puts into vacuum freeze drier and carries out freeze-drying, obtain graphene oxide powder;
It is characterized in that:
Step 8, the graphene oxide powder that step 7 is obtained, add 0.25 ~ 1L deionized water by every 1g and be mixed with graphene oxide dispersion, stir 6 ~ 12h with 50 ~ 150rpm, add 0.5 ~ 4g vulcanized sodium with every 1g graphene oxide powder or 0.5 ~ 4g ascorbic acid becomes mixed liquor as reducing agent;
Step 9, the mixed liquor obtained by step 8, after stirring 1 ~ 10min with 50 ~ 150rpm, after leaving standstill 0.5 ~ 36h, poured into by mixed liquor in shaped samples bottle corresponding to electrode shape, sealing, heating-up temperature is 80 ~ 95 DEG C, and heating time is 3 ~ 10h; The black solid deionized water taken out in sample bottle soaks, and the time of immersion is not less than 20h, obtains Graphene hydrogel electrode.
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