CN102956864B - A kind of preparation method of nitrating Graphene electrodes - Google Patents
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Abstract
The invention provides a kind of preparation method of nitrating Graphene electrodes, the step comprised has: obtain graphene oxide suspension; Described graphene oxide suspension is mixed with metal salt solution, is mixed with electrolyte; At least one pair of electrode slice be connected with direct current is put into described electrolyte, connects direct current and carry out electrophoresis, obtain the electrode slice that surface deposition has graphene oxide, and dry under vacuum; The graphene oxide of dried described electrode slice surface deposition and ammonia are carried out N doping reaction, obtains nitrating Graphene electrodes precursor; Under hydrogen shield, described nitrating Graphene electrodes precursor and hydrogen are carried out reduction reaction, obtain the nitrating Graphene electrodes of described low oxygen content.Preparation method's technique of nitrating Graphene electrodes of the present invention is simple, and efficiency is high, and cost is low, and nitrating Graphene electrodes equivalent series resistance prepared by the method is low, and conductivity is high, and the nitrating Graphene oxygen content in nitrating Graphene electrodes is low.
Description
Technical field
The invention belongs to electrode technology field, specifically a kind of preparation method of nitrating Graphene electrodes.
Background technology
Since strong K sea nurse (AndreK.Geim) of the peace moral of Univ Manchester UK etc. prepared grapheme material in 2004, pay attention to widely because the structure of its uniqueness and photoelectric property receive people.Single-layer graphene due to its large specific area, excellent conduction, heat conductivility and low thermal coefficient of expansion and be considered to desirable material.As: 1. high strength, Young mole (1,100GPa), fracture strength: (125GPa); 2. high heat conductance (5,000W/mK); 3. high conductivity, carrier transport rate (200,000cm
2/ Vs); 4. high specific area (calculated value: 2,630m
2/ g).Especially its high connductivity character, the structural property of the nanoscale of large specific surface character and its monolayer two dimension, can be used as electrode material in ultracapacitor and lithium ion battery.
At present, the technique that tradition prepares electrode slice (comprising Graphene electrodes sheet) is comparatively complicated, and adds certain binding agent, increases the equivalent series resistance of electrode slice, affects the power density of ultracapacitor.And when graphite oxide is reduced into Graphene, general oxygen content, also about 10%, like this, when it can be used as electrode material, makes its conductivity and electrochemical stability aspect have certain restriction.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, there is provided a kind of technique simple, efficiency is high, the preparation method of the nitrating Graphene electrodes that cost is low, nitrating Graphene electrodes equivalent series resistance prepared by the method is low, conductivity is high, and the nitrating Graphene oxygen content in nitrating Graphene electrodes is low.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
A preparation method for nitrating Graphene electrodes, comprises the steps:
Obtain graphene oxide suspension;
Described graphene oxide suspension is mixed with metal salt solution, is mixed with electrolyte;
At least one pair of electrode slice be connected with direct current is put into described electrolyte, connects direct current and carry out electrophoresis, obtain the electrode slice that surface deposition has graphene oxide, and dry under vacuum;
The graphene oxide of dried described electrode slice surface deposition and ammonia are carried out N doping reaction, obtains nitrating Graphene electrodes precursor;
Under hydrogen shield, described nitrating Graphene electrodes precursor and hydrogen are carried out reduction reaction, obtain described nitrating Graphene electrodes.
The preparation method of above-mentioned nitrating Graphene electrodes at least has the following advantages:
1. adopt the method for electro-deposition, make to be deposited directly on electrode slice containing graphene oxide composite material, graphene oxide obtains nitrating Graphene electrodes after N doping, reduction, this method avoid binding agent to use, thus effectively reduce the equivalent series resistance (ESR) of this nitrating Graphene electrodes, when by nitrating Graphene electrodes for the preparation of ultracapacitor time, can the power density of more effective raising ultracapacitor;
2. graphene oxide is deposited directly on electrode slice, carry out nitrating again and reduction obtains nitrating Graphene electrodes, thus simplify the preparation technology of this nitrating Graphene electrodes, improve production efficiency and business efficiency, effectively overcome the deficiency that tradition prepares electrode process complexity;
3. graphene oxide is deposited directly on electrode slice, then carries out nitrating and reduction obtains nitrating Graphene electrodes, thus significantly improve this nitrating Graphene electrodes electrical conductance, also enhance the stability of this nitrating Graphene electrodes simultaneously;
4. the nitrating Graphene in nitrating Graphene electrodes is first reduced by ammonia doping by graphene oxide, prepared by hydrogen reducing again, greatly reduced the content of oxygen in nitrating Graphene by 2 footwork reduction, make the nitrating graphene-structured of generation more stable, conductivity is high;
Accompanying drawing explanation
Fig. 1 is the process flow diagram of embodiment of the present invention nitrating Graphene electrodes preparation method;
Fig. 2 is the scanning of scanning electron microscope figure of nitrating Graphene electrodes prepared by the embodiment of the present invention 1.
Fig. 3 is the constant current charge-discharge lab diagram of button cell under electric current is 1A/g prepared by application example of the present invention.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is described in further detail.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiments provide a kind of technique simple, efficiency is high, the preparation method of the nitrating Graphene electrodes that cost is low.The technological process of this nitrating Graphene electrodes preparation method as shown in Figure 1, specifically comprises the steps:
S1: obtain graphene oxide suspension;
S2: described graphene oxide suspension is mixed with metal salt solution, is mixed with electrolyte;
S3: at least one pair of electrode slice be connected with direct current is put into described electrolyte, connects direct current and carries out electrophoresis, obtain the electrode slice that surface deposition has graphene oxide, and dry under vacuum;
S4: the graphene oxide of dried described electrode slice surface deposition and ammonia are carried out N doping reaction, obtains nitrating Graphene electrodes precursor;
S5: under hydrogen shield, carries out reduction reaction by described nitrating Graphene electrodes precursor and hydrogen, obtains the nitrating Graphene electrodes of low oxygen content.
Particularly, in above-mentioned steps S1, graphene oxide suspension preferably obtains as follows: will prepare graphite oxide and the dispersant of acquisition in advance, and under hyperacoustic effect, obtain described graphene oxide suspension.Wherein, this dispersant is preferably alcohol, as ethanol, propyl alcohol etc., can certainly be other organic solvents such as benzene, oxolane; The time of this hyperacoustic effect is preferably 30 ~ 60 minutes.
In method prepared by above-mentioned graphene oxide suspension, the preparation method of graphite oxide can obtain graphite oxide according to the hummers method improved, concrete see the step S11 in embodiment 1.Before this graphite oxide and dispersant, also can by the graphite oxide of acquisition in advance at vacuum condition and 500 ~ 800 DEG C the heat treated time be preferably 5 ~ 30 seconds.Such heat treatment can make graphite oxide under the action of heat, discharge portion gas, make graphite oxide spacing increase between layers, be easier to peel off into monolithic, thus the time of ultrasonic wave process can be shortened, further energy efficient, boosts productivity and production cost, makes the area of graphene oxide lamella keep larger simultaneously.In addition, the concentration of this graphene oxide suspension can be allocated flexibly according to actual conditions, is not particularly limited and requires the present invention.
Further preferably, above-mentioned graphene oxide suspension comprises carbon nano-tube further, and the mass ratio of this carbon nano-tube and graphene oxide is preferably 1: 2 ~ 1, is more preferably 1: 1.The compound method that should contain the graphene oxide suspension of carbon nano-tube is: first take each component by both preferred proportions, mix to add or join in dispersant respectively again and mix, under hyperacoustic effect, obtain the graphene oxide suspension containing carbon nano-tube.
Further preferably, carbon nano-tube is acidifying nanotube, and this acidifying carbon nano-tube refers to the carbon nano-tube after peracid treatment, and the acid treatment step of this nanotube is:
Carbon nano-tube is added in acid solution, under 60 DEG C of-90 DEG C of conditions, adds hot reflux 1 hour ~ 3 hours.Filter, washing and drying.This acid is restriction not, such as, and watery hydrochloric acid, dilute sulfuric acid, dust technology etc.; By carbon nano-tube is used acid solution immersion treatment, carbon nano tube surface functional group (as OH, COOH) quantity is increased greatly.
Particularly, in above-mentioned steps S2, in the electrolytic solution, the mass ratio of graphene oxide and slaine is 1: 1 ~ 2.Wherein, the slaine in this metal salt solution is Mg (NO
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o, Zn (NO
3)
26H
2at least one in O; The concentration of this metal salt solution can be prepared flexibly according to needs of production, but preferably should ensure both content described above in the electrolytic solution, and the concentration of metal salt solution is 0.2mg/ml ~ 0.5mg/ml.
Further, in above-mentioned steps S2, after graphene oxide suspension being mixed with metal salt solution, also preferably adopt ultrasonic wave to this mixed liquor process 15min ~ 60min.Like this, the more even of the dispersion of raising graphene oxide and slaine is conducive to.
Or further, when carbon nano-tube containing, for example the content described in above-mentioned steps S1 in graphene oxide suspension, after graphene oxide suspension containing carbon nano-tube being mixed with metal salt solution, also preferably adopt ultrasonic wave to this mixed liquor process 15min ~ 60min.
Particularly, in above-mentioned steps S3, the preferred 40V ~ 80V of direct voltage that these two paired electrode slices are electrically connected, and the preferred 0.5cm ~ 1cm of spacing between two paired electrode slices, be more preferably 0.5cm, the preferred 5min ~ 20min of electrophoresis time.Spacing between these preferred electrophoretic voltage and two paired electrode slices can better improve electrophoresis efficiency, improves the speed of graphene oxide at electrode slice surface deposition.This preferred electrophoresis time makes the thickness of the graphene oxide layer of electrode slice surface deposition suitable, thus while guarantee nitrating Graphene electrodes performance, reduces production cost.This electrode slice can select nickel foil electrode slice, foil electrode sheet, corrosive aluminum foil electrode slice or copper foil electrode sheet, and the diameter of this electrode slice is 5cm ~ 10cm.Certainly, can also according to the concrete needs produced, flexibly to the shape of electrode, size and kind make suitable replacement or change.
In this step S3, after electrophoresis, reply electrode slice carries out drying, in order to ensure performance stable in dry run of the electrode slice after this electrophoresis, should carry out drying at vacuum condition, dry removing simultaneously sticks to surface deposition volatile material on the electrode slice of graphene oxide.Dry mode preferably but after being not only only and first naturally drying, then toasts 1 ~ 3 hour.The temperature of toasting according to this area is conventional is carried out.
Further preferably, when the electrolyte in above-mentioned steps S2 is the graphene oxide containing carbon nano-tube, in electrophoresis process, carbon nano-tube carries out electrophoresis, at electrode slice surface deposition together with graphene oxide in company with graphene oxide.
Particularly, in above-mentioned steps S4, the flow of the ammonia of gaseous state is preferably 50ml/min ~ 80ml/min.The temperature that graphene oxide and ammonia carry out N doping reaction is preferably 500 DEG C ~ 800 DEG C, and the reaction time is preferably 2 ~ 4 hours.This preferred ammonia usage, the content of nitrogen element in the nitrating Graphene generated can be made at a best content range, thus improve the electrochemical stability performance of this nitrating Graphene further, make the graphene oxide of electrode slice surface deposition and ammonia fully react simultaneously, improve the utilance of reactant, thus further reduce production cost.Fully react both the preferred time that this graphene oxide electrode and ammonia carry out reacting can ensure, make the graphene oxide nitrating in graphene oxide electrode appropriate.
Further preferably, when electrode slice deposited on silicon prepared by above-mentioned steps S3 has graphene oxide and carbon nano-tube mixed layer, occur under these 500 DEG C ~ 800 DEG C conditions in N doping course of reaction, carbon nano-tube can effectively be inserted between graphene layer; Or the functional group in carbon nano-tube and the functional group on Graphene react mutually, carbon nano-tube is made to be grafted on graphenic surface, Graphene is separated from each other out between layers, Graphene specific area is increased to reach, effectively avoid the generation of Graphene reunion and lamination, and then increase the object of the product containing this nitrating Graphene electrodes as the ratio capacitance of ultracapacitor.
This is because, inventor finds in the process of research, when the nitrating Graphene electrodes prepared by step S5 is carried out in dry process, the two-dimensional structure of Graphene lose in drying in the water process of interlayer be easy to occur reunite and stacked, curling or height fold, finally cause the utilance of its specific area to reduce, thus finally have impact on the ratio capacitance of the product containing this nitrating Graphene electrodes as ultracapacitor.Inventor studies discovery further, when mixing carbon nano-tube in the graphene oxide of electrode slice surface deposition prepared by step S3, can effectively solve this difficult problem, this carbon nano-tube effectively can avoid the generation of Graphene reunion and lamination, effective raising Graphene specific area.Further study discovery, when the mass ratio of carbon nano-tube and graphene oxide is preferably 1: 2 ~ 1, Graphene reunite and the probability minimum Graphene specific area of lamination phenomenon generation relative larger.
Particularly, in above-mentioned steps S5, the temperature of reduction reaction is preferably 500 DEG C ~ 800 DEG C, and the time of reaction is preferably 1 ~ 2 hour.This preferred reducing condition, is ensureing that under the prerequisite that nitrating graphene oxide fully reduces, energy efficient, reduces production cost further, meanwhile, improves the efficiency of reduction reaction.
Therefore, the preparation method of above-mentioned nitrating Graphene electrodes adopts the method for electro-deposition, make to be deposited directly on electrode slice containing graphene oxide composite material, graphene oxide obtains nitrating Graphene electrodes after N doping, reduction, this method avoid binding agent to use, thus effectively reduce the equivalent series resistance (ESR) of this nitrating Graphene electrodes, when by nitrating Graphene electrodes for the preparation of ultracapacitor time, can the power density of more effective raising ultracapacitor; Graphene oxide is deposited directly on electrode slice, carry out nitrating again and reduction obtains nitrating Graphene electrodes, thus simplify the preparation technology of this nitrating Graphene electrodes, improve production efficiency and business efficiency, effectively overcome the deficiency that tradition prepares electrode process complexity, also significantly improve this nitrating Graphene electrodes electrical conductance simultaneously, enhance the stability of this nitrating Graphene electrodes; Nitrating Graphene in nitrating Graphene electrodes is first reduced by ammonia doping by graphene oxide, prepared by hydrogen reducing again, greatly reduced the content of oxygen in nitrating Graphene by 2 footwork reduction, make the nitrating graphene-structured of generation more stable, conductivity is high.
Now for concrete nitrating Graphene electrodes preparation method, the present invention is further elaborated.
Embodiment 1
A preparation method for nitrating Graphene electrodes, comprises following processing step:
S11: the preparation of graphite oxide: be that 100 object natural flake graphite powder join 0 DEG C by 0.5g particle diameter, in the concentrated sulfuric acid of 11.5mL, add 1.5g potassium permanganate again, the temperature of mixture remains on less than 10 DEG C, stir 2h, then after room-temperature water bath stirs 24h, 46mL deionized water is slowly added under condition of ice bath, after 15min, then 140mL deionized water (wherein containing 2.5mL concentration is the hydrogen peroxide of 30%) is added, after thing color to be mixed becomes glassy yellow, carry out suction filtration, finally wash with the hydrochloric acid that 250ml concentration is 10%, after suction filtration, namely graphite oxide is obtained at 60 DEG C of vacuumize 48h.
S12: the preparation of graphene oxide suspension: add in ethanol by the graphite oxide in step S11, ultrasonic disperse can obtain graphene oxide suspension in 30 minutes.
S13: surface deposition has the nickel electrode of graphene oxide to prepare: first add Mg (NO in the graphene oxide suspension of S12 gained
3)
26H
2o solution (concentration is 0.2mg/ml), ultrasonic 15min, to obtain even electrolyte, and makes in this electrolyte, graphene oxide and Mg (NO
3)
26H
2the mass ratio of O is 1: 1, be placed in electrolyte with the nickel foil electrode runs parallel symmetry of a pair 5cm diameter again, the direct current of 40V is added between two nickel foil electrodes, the spacing of two nickel foil electrodes is 0.5cm, electrophoresis 5min, obtain the nickel electrode that surface deposition has graphene oxide, after then this electrode being dried naturally, vacuum bakeout 1 hour at 60 DEG C.
S14: the preparation of nitrating Graphene electrodes precursor: had by the surface deposition of drying the nickel electrode of graphene oxide be put into the centre of heating furnace pipe and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, control the flow of ammonia at 80ml/min, pass into ammonia 5 minutes, the air in tube furnace is discharged, then stove is heated, reaction temperature 500 DEG C is warming up to the rate of heat addition of 10 DEG C/min, keep 2h, after completion of the reaction, cool to room temperature in ammonia atmosphere.
S15: the preparation of nitrating Graphene electrodes: pass into hydrogen in tube furnace, deaeration, then stove is heated, be warming up to reaction temperature 500 DEG C with the rate of heat addition of 10 DEG C/min, keep 1h, then cool, stop passing into hydrogen, obtain the nitrating Graphene electrodes of low oxygen content.
The nitrating Graphene electrodes prepared by the present embodiment 1 carries out electron scanning micrograph analysis, and its profile picture as shown in Figure 2.As shown in Figure 2, nitrating Graphene prepared by the present embodiment 1 completely covers electrode slice, is well deposited on electrode slice.
The nitrating Graphene that the nitrating Graphene electrodes prepared by the present embodiment 1 deposits carries out elementary analysis, and analysis result is: C element content is 94.6%, and N element content is 2.5%, O constituent content is 2.3%, other elements 0.6%.With reduce according to existing general hydrazine hydrate etc. the Graphene prepared amount of oxidation (about 10%) compared with, nitrating Graphene oxygen content prepared by the present embodiment is low.
Embodiment 2
A preparation method for nitrating Graphene electrodes, comprises following processing step:
S21: the preparation of graphite oxide: be that 500 object natural flake graphite powder join 0 DEG C by 0.5g particle diameter, in the concentrated sulfuric acid of 11.5mL, add 1.5g potassium permanganate again, the temperature of mixture remains on less than 10 DEG C, stir 2h, then after room-temperature water bath stirs 24h, 46mL deionized water is slowly added under condition of ice bath, after 15min, then 140mL deionized water (wherein containing 2.5mL concentration is the hydrogen peroxide of 30%) is added, after thing color to be mixed becomes glassy yellow, carry out suction filtration, finally wash with the hydrochloric acid that 250ml concentration is 10%, after suction filtration, namely graphite oxide is obtained at 60 DEG C of vacuumize 48h.
S22: the preparation of graphene oxide suspension: add in isopropyl alcohol by the graphite oxide in step S21, ultrasonic disperse can obtain graphene oxide suspension in 30 minutes.
S23: surface deposition has the nickel electrode of graphene oxide to prepare: first add Mg (NO in the graphene oxide suspension of S22 gained
3)
26H
2o solution (concentration is 0.2mg/ml), ultrasonic 15min, to obtain even electrolyte, and makes in this electrolyte, graphene oxide and Mg (SO
4)
27H
2the mass ratio of O is 1: 2, be placed in electrolyte with two to the nickel foil electrode slice Parallel Symmetric of parallel connection again, the direct current of 40V is added respectively between paired electrode sheet, the spacing of two paired electrode slices is 0.5cm, electrophoresis 5min, obtain the nickel electrode that surface deposition has graphene oxide, after then this nickel electrode being dried naturally, vacuum bakeout 3 hours at 60 DEG C.
S24: the preparation of nitrating Graphene electrodes precursor: had by the surface deposition of drying the nickel electrode of graphene oxide be put into the centre of heating furnace pipe and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, control the flow of ammonia at 80ml/min, pass into ammonia 10 minutes, the air in tube furnace is discharged, then stove is heated, reaction temperature 500 DEG C is warming up to the rate of heat addition of 10 DEG C/min, keep 4h, after completion of the reaction, cool to room temperature in ammonia atmosphere.
S25: the preparation of nitrating Graphene electrodes: pass into hydrogen in tube furnace, deaeration, then stove is heated, be warming up to reaction temperature 500 DEG C with the rate of heat addition of 10 DEG C/min, keep 1h, then cool, stop passing into hydrogen, obtain nitrating Graphene electrodes.
Embodiment 3
A preparation method for Graphene electrodes, comprises following processing step:
S31: the preparation of graphite oxide: see the step S11 of embodiment 1.
S32: the preparation of graphene oxide suspension: add in oxolane by the graphite oxide in step S31, ultrasonic disperse 2 hours, to graphene oxide suspension.
S33: surface deposition has the nickel electrode of graphene oxide to prepare: first add Mg (NO in the graphene oxide suspension of S32 gained
3)
26H
2o solution (concentration is 0.5mg/ml), ultrasonic 60min, to obtain even electrolyte, and makes in this electrolyte, graphene oxide and Fe (NO
3)
39H
2the mass ratio of O is 1: 1, be placed in electrolyte with the nickel foil electrode runs parallel symmetry of a pair 10cm diameter again, the direct current of 80V is added between a pair nickel foil electrode, the spacing between electrodes of a pair nickel foil electrode is 0.5cm, electrophoresis 20min, obtain the nickel electrode that surface deposition has graphene oxide, after then this nickel electrode being dried naturally, vacuum bakeout 3 hours at 60 DEG C.
S34: the preparation of nitrating Graphene electrodes precursor: had by the surface deposition of drying the nickel electrode of graphene oxide be put into the centre of heating furnace pipe and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, control the flow of ammonia at 80ml/min, pass into ammonia 10 minutes, the air in tube furnace is discharged, then stove is heated, reaction temperature 800 DEG C is warming up to the rate of heat addition of 10 DEG C/min, keep 2h, after completion of the reaction, cool to room temperature in ammonia atmosphere.
S35: the preparation of nitrating Graphene electrodes: pass into hydrogen in tube furnace, deaeration, then stove is heated, be warming up to reaction temperature 800 DEG C with the rate of heat addition of 10 DEG C/min, keep 2h, then cool, stop passing into hydrogen, obtain nitrating Graphene electrodes.
Embodiment 4
A preparation method for Graphene electrodes, comprises following processing step:
S41: the preparation of graphite oxide: see the step S21 in embodiment 2.
S42: the preparation of graphene oxide suspension: add in propyl alcohol by the graphite oxide powder in step S41, ultrasonic disperse can obtain graphene oxide suspension in 30 minutes.
S43: surface deposition has the corrosive aluminum foil electrode of graphene oxide to prepare: first add Zn (NO in the graphene oxide suspension of S42 gained
3)
26H
2o solution (concentration is 0.5mg/ml), ultrasonic 30min, to obtain even electrolyte, and makes in this electrolyte, graphene oxide and Zn (NO
3)
26H
2the mass ratio of O is 1: 2, be placed in electrolyte with three to the corrosive aluminum foil electrode runs parallel symmetry of the 7cm diameter of parallel connection again, the direct current of 60V is added between two paired corrosive aluminum foil electrodes, the spacing of two paired corrosive aluminum foil electrodes is 0.5cm, electrophoresis 12min, obtain the corrosive aluminum foil electrode that surface deposition has graphene oxide, after then this corrosive aluminum foil electrode being dried naturally, vacuum bakeout 3 hours at 60 DEG C.
S44: the preparation of nitrating Graphene electrodes precursor: had by the surface deposition of drying the corrosive aluminum foil electrode of graphene oxide be put into the centre of heating furnace pipe and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, control the flow of ammonia at 80ml/min, pass into ammonia 10 minutes, air in tube furnace is discharged, then stove is heated, reaction temperature 650 DEG C is warming up to the rate of heat addition of 10 DEG C/min, keep 2h, after completion of the reaction, cool to room temperature in ammonia atmosphere.
S45: the preparation of low oxygen content nitrating Graphene electrodes: pass into hydrogen in tube furnace, deaeration, then stove is heated, be warming up to reaction temperature 650 DEG C with the rate of heat addition of 10 DEG C/min, keep 1h, then cool, stop passing into hydrogen, obtain nitrating Graphene corrosive aluminum foil electrode.
Embodiment 5
A preparation method for Graphene electrodes, comprises following processing step:
S51: the preparation of graphite oxide: see the step S21 in embodiment 2.
S52: the preparation of the graphene oxide suspension containing carbon nano-tube: by the carbon nano-tube after the graphene oxide in step S51 and acidified process by weight 1: 1 ratio add in ethanol, ultrasonic disperse can obtain the graphene oxide suspension containing carbon nano-tube for 30 minutes, the step of the carbon nano-tube after acidified process is, carbon nano-tube is added in dilute hydrochloric acid solution, under 90 DEG C of conditions, adds hot reflux 3 hours.
S53: surface deposition contains the copper foil electrode preparation of the graphene oxide of carbon nano-tube: elder generation adds Mg (NO to containing in the graphene oxide suspension of carbon nano-tube of S42 gained
3)
26H
2o solution (concentration is 0.5mg/ml), ultrasonic 15min, to obtain even electrolyte, and makes in this electrolyte, graphene oxide and carbon nano-tube and Mg (NO
3)
26H
2the mass ratio of O is 1: 1, be placed in electrolyte with three to the copper foil electrode Parallel Symmetric of the 5cm diameter of parallel connection again, the direct current of 40V is added between two paired copper foil electrodes, the spacing of two paired copper foil electrodes is 0.5cm, electrophoresis 5min, obtain the copper foil electrode that surface deposition contains the graphene oxide of carbon nano-tube, after then this copper foil electrode being dried naturally, vacuum bakeout 3 hours at 60 DEG C.
S54: nitrating contains the preparation of the Graphene electrodes precursor of carbon nano-tube: had by the surface deposition of drying the graphene oxide copper foil electrode containing carbon nano-tube be put into the centre of heating furnace pipe and pass to highly purified ammonia, the flow of ammonia is controlled by gas flowmeter, control the flow of ammonia at 80ml/min, pass into ammonia 10 minutes, air in tube furnace is discharged, then stove is heated, reaction temperature 500 DEG C is warming up to the rate of heat addition of 10 DEG C/min, keep 2h, after completion of the reaction, cool to room temperature in ammonia atmosphere.
S55: low oxygen content nitrating contains the preparation of the Graphene electrodes of carbon nano-tube: pass into hydrogen in tube furnace, deaeration, then stove is heated, reaction temperature 500 DEG C is warming up to the rate of heat addition of 10 DEG C/min, keep 1h, then cool, stop passing into hydrogen, obtain the Graphene electrodes that nitrating contains carbon nano-tube.
Embodiment 6
A kind of preparation method of the Graphene electrodes containing carbon nano-tube, see the preparation process of the Graphene electrodes of embodiment 5 containing carbon nano-tube, difference is, in the process for preparation of the graphene oxide suspension containing carbon nano-tube, the carbon nano-tube after graphite oxide powder and acidified process by weight 2: 1 ratio add in isopropyl alcohol.
Application example
The application of Graphene electrodes in button cell prepared by above-described embodiment 5, this button cell is prepared as follows:
The pole piece roller mill prepared by above-described embodiment 5 carries out roll extrusion, the pole piece card punch of roll-in is broken into the circular pole piece that diameter is 10mm, correct amount.
The assembling of battery: by pole piece in glove box, barrier film and electrolyte assemble according to cell making process, its septation is celgard2000, electrolyte is the 1-ethyl-3-methylimidazole tetrafluoro boric acid salting liquid of 0.5mol/L, assemble rear leaving standstill and carry out constant current charge-discharge test after one day, wherein voltage range is 0-1.85V, and electric current is that 1A/g carries out constant current charge-discharge.
This charging and discharging curve as shown in Figure 3, as shown in Figure 3, each complete circulation is symmetrical, and efficiency for charge-discharge can reach 98%, calculated from the power density formula of ultracapacitor, the power density of this ultracapacitor obtains significant raising.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for nitrating Graphene electrodes, comprises the steps:
Obtain graphene oxide suspension, wherein, described graphene oxide suspension comprises carbon nano-tube further, and described carbon nano-tube is acidifying carbon nano-tube;
Described graphene oxide suspension is mixed with metal salt solution, is mixed with electrolyte;
At least one pair of electrode slice be connected with direct current is put into described electrolyte, connects direct current and carry out electrophoresis, obtain the electrode slice that surface deposition has graphene oxide, and dry under vacuum;
The graphene oxide of dried described electrode slice surface deposition and ammonia are carried out N doping reaction, obtains nitrating Graphene electrodes precursor;
Under hydrogen shield, described nitrating Graphene electrodes precursor and hydrogen are carried out reduction reaction, obtain described nitrating Graphene electrodes.
2. the preparation method of nitrating Graphene electrodes according to claim 1, is characterized in that: the mass ratio of described acidifying carbon nano-tube and graphene oxide is 1:2 ~ 1.
3. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, is characterized in that: in described electrolyte, and the mass ratio of graphene oxide and slaine is 1:1 ~ 2.
4. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, is characterized in that: the slaine in described metal salt solution is Mg (NO
3)
26H
2o, Mg (SO
4)
27H
2o, Fe (NO
3)
39H
2o, Zn (NO
3)
26H
2at least one in O.
5. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, is characterized in that: in described electrolyte, and the concentration of slaine is 0.2mg/ml ~ 0.5mg/ml.
6. the preparation method of nitrating Graphene electrodes according to claim 1, is characterized in that: the direct voltage that described two electrode slices in pairs connect is 40V ~ 80V, and the spacing of described two electrode slices is in pairs 0.5cm ~ 1cm; The time of described electrophoresis is 5min ~ 20min.
7. the preparation method of the nitrating Graphene electrodes according to claim 1 or 6, is characterized in that: described electrode slice is the nickel foil of 5cm ~ 10cm diameter, aluminium foil or Copper Foil.
8. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, is characterized in that: described graphene oxide and ammonia carry out in the process of N doping reaction, and the flow of ammonia is 50ml/min ~ 80ml/min.
9. the preparation method of nitrating Graphene electrodes according to claim 8, is characterized in that: the temperature that described graphene oxide and ammonia carry out N doping reaction is 500 DEG C ~ 800 DEG C, and the reaction time is 2 ~ 4 hours.
10. the preparation method of nitrating Graphene electrodes according to claim 1 and 2, is characterized in that: the temperature of described reduction reaction is 500 DEG C ~ 800 DEG C, and the time of reaction is 1 ~ 2 hour.
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|---|---|---|---|
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| CN103311502A (en) * | 2013-05-08 | 2013-09-18 | 上海新池能源科技有限公司 | Metal foil/graphene composite electrode plate and preparation method thereof |
| CN104477895A (en) * | 2014-12-11 | 2015-04-01 | 百顺松涛（天津）动力电池科技发展有限公司 | Preparation method of nitrogen-doped graphene for cathode of lithium ion battery |
| CN105185605B (en) * | 2015-08-27 | 2017-11-10 | 长春工业大学 | Load the electrode preparation method of graphene/metallic compound |
| TWI639555B (en) * | 2016-05-27 | 2018-11-01 | 國立交通大學 | Preparation method of nitrogen-doped graphene |
| CN107359337A (en) * | 2017-07-12 | 2017-11-17 | 湖南艾威尔新能源科技有限公司 | The preparation method of graphene combination electrode piece |
| EP3447026A1 (en) * | 2017-08-24 | 2019-02-27 | RD Graphene Limited | 3d graphene |
| CN107644743A (en) * | 2017-08-25 | 2018-01-30 | 天津大学 | A kind of preparation method of the three-dimensional porous nitrogen-doped graphene of self-supporting-nickel hydroxide electrochemical capacitance electrode material |
| CN110289179B (en) * | 2019-05-29 | 2021-07-13 | 南京源恒能源科技有限公司 | Preparation method of active metal oxide-carbonized bacterial cellulose electrode material |
| CN111215111B (en) * | 2020-01-13 | 2022-07-19 | 山西大学 | Carbon dioxide electrochemical reduction catalyst rich in oxygen vacancies and preparation method and application thereof |
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| CN101734650A (en) * | 2009-12-23 | 2010-06-16 | 沈阳建筑大学 | Method for preparing graphene-carbon nano tube hybrid composite |
| CN102013330A (en) * | 2010-11-16 | 2011-04-13 | 浙江大学 | Film for graphene/porous nickel oxide composite super capacitor and preparation method thereof |
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| CN102034975A (en) * | 2010-11-15 | 2011-04-27 | 中国科学院青岛生物能源与过程研究所 | Nitrogen-doped graphite carbon serving as anode material of lithium ion battery, and preparation method and application thereof |
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