CN106783237B - A kind of Co-Fe alloy/graphite alkene composite material and preparation method and application - Google Patents
A kind of Co-Fe alloy/graphite alkene composite material and preparation method and application Download PDFInfo
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Abstract
The invention belongs to electrochemical technology field, a kind of Co-Fe alloy/graphite alkene composite material and preparation method and application are disclosed.By graphene oxide ultrasonic disperse in water；At room temperature, by 1,1 '-ferrocenecarboxylic acid and four hydration cobalt acetate stirring and dissolvings in graphene oxide dispersion；Temperature control adds alkali into acquired solution at 20 ~ 80 DEG C while stirring, and the pH for adjusting solution is 4 ~ 12, is stirred for 2 ~ 10 h；Gained system is transferred in water heating kettle, 40 ~ 200 DEG C of 48 ~ 72h of hydro-thermal, after being cooled to room temperature, takes out reaction solution, isolated sediment is baked to；Grinding calcines 2 ~ 8h in a nitrogen atmosphere by ground powder, at 400 ~ 600 DEG C to get Co-Fe alloy/graphite alkene composite material.The present invention passes through the preparation of Co-Fe alloy/graphite alkene composite material, and as the electrode material of supercapacitor, the chemical property of capacitor has obtained great promotion, has very vast potential for future development.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of Co-Fe alloy/graphite alkene composite material and its preparation
Methods and applications.
Background technique
Graphene is a kind of two-dimensional sheet material, has high specific surface area and excellent electric conductivity, in electrochemical field
It has a wide range of applications, after Co-Fe alloy and graphene combination, substantially increases its chemical property.It is with graphene at present
The method of substrate composition metal alloy mainly has：Mechanical mixing, in situ synthesis etc..It is mechanical for first two method
Mixing method implementation process is simple, but is not readily available the uniform composite material of combined state；And growth in situ rule is to operation
Condition has very high requirement, and the nano particle being prepared also is easy to reunite.
Supercapacitor（Or electrochemical capacitor）, already become a nova in energy storage device field, and close
The very big concern of scientific research personnel is obtained over year.It, can be by electrochemical capacitor at present according to surface chemistry and physics energy storage mechnism
Device is divided into two classes：One kind is double layer capacitor（EDLC）, electrode material is made of the carbon material with high surface area；It is another
Class is pseudocapacitors（pseudocapacitor）, energy storage mechnism be based on oxidation-reduction reaction realize energy storage, such as
Conducting polymer and transition metal oxide.Electrochemical capacitor based on graphene mainly improves capacitive character in terms of two
Can, i.e. the exploitation of new material and the potential basal energy Storage mechanism of exploration.
Summary of the invention
For the capacitive property for improving supercapacitor, the present invention sets about from the exploitation of new material, and it is an object of the present invention to provide a kind of
Co-Fe alloy/graphite alkene composite material and preparation method, and apply it in supercapacitor.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of Co-Fe alloy/graphite alkene composite material, steps are as follows：
（1）, by graphene oxide ultrasonic disperse in water；
（2）, at room temperature, by 1,1 '-ferrocenecarboxylic acid and four hydration cobalt acetate stirring and dissolvings in step（1）Gained
Graphene oxide dispersion in；
（3）, temperature control at 20 ~ 80 DEG C, to step（2）Adding alkali in acquired solution while stirring, the pH for adjusting solution is 4 ~ 12,
It is stirred for 2 ~ 10 h；
（4）, by step（3）Gained system is transferred in water heating kettle, 40 ~ 200 DEG C of 48 ~ 72h of hydro-thermal, after being cooled to room temperature,
Reaction solution is taken out, isolated sediment is baked to；
（5）, grinding steps（4）Gained sediment after drying, in a nitrogen atmosphere by ground powder, 400 ~ 600 DEG C
2 ~ 8h of lower calcining is to get Co-Fe alloy/graphite alkene composite material；
Wherein, based on mass volume ratio, graphene oxide: water: 1,1 '-ferrocenecarboxylic acid: four hydration cobalt acetate=0.2 ~
0.7g∶300~400mL∶1g∶1~9g。
Preferably, the alkali is sodium hydroxide, is added in the form of its aqueous solution, the concentration of sodium hydrate aqueous solution is 0.1 ~
0.5 mol/L。
Preferably, described to be separated into centrifuge separation, centrifugal rotational speed is 6000 ~ 8000r/min.
The Co-Fe alloy/graphite alkene composite material of the preparation method preparation.
Application of the Co-Fe alloy/graphite alkene composite material in supercapacitor.
Further, Co-Fe alloy/graphite alkene composite material is as electrode material.
Beneficial effect：
The present invention passes through the preparation of Co-Fe alloy/graphite alkene composite material, as the electrode material of supercapacitor
Material, the chemical property of capacitor have obtained great promotion, have very vast potential for future development.
Detailed description of the invention
Fig. 1：The infrared figure of Co-Fe alloy/graphite alkene composite material.
Fig. 2：The thermogravimetric analysis figure of Co-Fe alloy/graphite alkene composite material.
Fig. 3：The cyclic voltammogram of Co-Fe alloy/graphite alkene composite material.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, but protection scope of the present invention is not limited to
In this.
Embodiment 1
（1）Graphene oxide is prepared by improved Hummers method, by 300mg graphene oxide and 400mL deionization
Water mixing, the mixture that the two is obtained carry out ultrasonic disperse, and ultrasonic time is 6 h, shine solution with flashlight beam, and do not have
It was found that apparent particle aggregate, illustrates that graphene oxide is well dispersed in aqueous solution, to obtain finely dispersed yellowish-brown
Color graphene oxide dispersion；
（2）At room temperature, by four hydration acetic acid of the 1 of 1g yellowish-brown, 1 '-ferrocenecarboxylic acid powder and 1g pink
Cobalt dust is dissolved in step（1）In resulting graphene oxide dispersion, stirring, until solid all dissolves, solution is by yellowish-brown
Become dark red；
（3）By step（2）Gained brown solution is placed into temperature constant magnetic stirring water-bath, controls constant temperature water bath 70
DEG C, magnetic agitation is opened, sodium hydroxide solution is added dropwise in whipping process（0.1M）, the pH for adjusting solution is 6, is stirred for 8h；
（4）By step（3）Gained system is transferred in water heating kettle, and control temperature is at 45 DEG C, hydro-thermal 50h, after reaction,
Reaction solution is taken out from water heating kettle, repeatedly washing centrifugation（Control revolving speed is 6000r/min）, the sediment being centrifuged out is put in 60 DEG C
It is dried in baking oven, obtains Co-Fe alloy/graphite alkene composite material precursor；
（5）By step（4）Gained Co-Fe alloy/graphite alkene composite material precursor, is put in agate mortar, carefully grinds
Ground powder is transferred in porcelain boat by 0.5h, is placed in tube furnace under nitrogen atmosphere, with the heating rate of 10 DEG C/min
It is warming up at 500 DEG C and calcines 6h to get Co-Fe alloy/graphite alkene composite material.
The infrared figure of Co-Fe alloy/graphite alkene composite material obtained is as shown in Figure 1.Because calcining is not clean, can remain
Partial oxidation of graphite alkene, and contain a large amount of oxygen-containing functional group in graphene oxide, therefore, the Co-Fe alloy made from final/
Also it can contain a large amount of oxygen-containing functional group because of residual fraction graphene oxide in graphene composite material, as shown in Figure 1：3700
~3500 cm -1Between wide and strong absorption peak correspond to the stretching vibration of hydroxyl, 1723 cm-1Absorption peak correspond to carbonyl
The stretching vibration of base, 950 ~ 900 cm-1Absorption peak correspond to epoxy group stretching vibration, 780cm-1It is inhaled for the feature of Fe-O
Peak is received, in 564 cm-1With 667 cm-1For the characteristic absorption peak of Co-O, illustrate that foring stable Co-Fe alloy/graphite alkene answers
Condensation material.
Co-Fe alloy/graphite alkene composite material obtained is placed in air, with the heating rate of 10 DEG C/min by room
Temperature is warming up to 1000 DEG C of calcinings, obtains thermogravimetric curve, as shown in Figure 2.In curve, quality die-offs 37% at 300 ~ 410 DEG C, this
It is since graphene decomposition causes in composite material, curve tends towards stability after temperature is greater than 800 DEG C, illustrates that graphene divides completely
Solution.
Electrochemical property test：
Electrochemical Test Procedure is by working electrode, reference electrode, forms three electrode systems to electrode in electrochemical operation
It stands and carries out on (CHI760E), wherein electrolyte is the Na of 6mol/L2SO4Solution or KOH solution, sweep speed 50mv/s,
Co-Fe alloy/graphite alkene composite material is the active material of working electrode, and saturated calomel electrode (SCE) is reference electrode, platinum electricity
Extremely to electrode.Working electrode is made by following processes：
(1) slurrying：By Co-Fe alloy/graphite alkene composite material, binder (PTFE emulsions of 12 wt %) and conduction
Agent (Super P) is 8 in mass ratio:1:1 accurate weighing is added suitable dehydrated alcohol, is divided after 30 min of ultrasound
Dissipate uniform slurry；
(2) it is coated with：Slurry obtained is uniformly coated on the nickel foam disk (mm of r=7) for cutting out and weighing in advance；
(3) film-making：After the nickel foam coated is put into the sufficiently drying of 60 DEG C of baking oven, using twin rollers tabletting to get electricity
Pole piece（Working electrode）.
The cyclic voltammogram of acquisition is shown in Fig. 3.As shown in Figure 3：In Na2SO4When solution or KOH solution are as electrolyte, circulation
In voltammertry, obtained cyclic voltammogram presents more regular rectangle, presents the electric double layer capacitance characteristic of material.
Embodiment 2
（1）Graphene oxide is prepared by improved Hummers method, by 0.2mg graphene oxide and 300mL deionization
Water mixing, the mixture that the two is obtained carry out ultrasonic disperse, and ultrasonic time is 4 h, shine solution with flashlight beam, and do not have
It was found that apparent particle aggregate, illustrates that graphene oxide is well dispersed in aqueous solution, to obtain finely dispersed yellowish-brown
Color graphene oxide dispersion；
（2）At room temperature, by four hydration acetic acid of the 1 of 1g yellowish-brown, 1 '-ferrocenecarboxylic acid powder and 5g pink
Cobalt dust is dissolved in step（1）In resulting graphene oxide dispersion, stirring, until solid all dissolves, solution is by yellowish-brown
Become dark red；
（3）By step（2）Gained brown solution is placed into temperature constant magnetic stirring water-bath, controls constant temperature water bath 30
DEG C, magnetic agitation is opened, sodium hydroxide solution is added dropwise in whipping process（0.3M）, the pH for adjusting solution is 4, is stirred for 2h；
（4）By step（3）Gained system is transferred in water heating kettle, controls temperature at 100 DEG C, hydro-thermal 48h, reaction terminates
Afterwards, reaction solution is taken out from water heating kettle, repeatedly washing centrifugation（Control revolving speed is 7000r/min）, the sediment being centrifuged out is put in
It is dried in 40 DEG C of baking ovens, obtains Co-Fe alloy/graphite alkene composite material precursor；
（5）By step（4）Gained Co-Fe alloy/graphite alkene composite material precursor, is put in agate mortar, carefully grinds
Ground powder is transferred in porcelain boat by 0.5h, is placed in tube furnace under nitrogen atmosphere, with the heating rate of 10 DEG C/min
It is warming up at 400 DEG C and calcines 4h to get Co-Fe alloy/graphite alkene composite material.
Embodiment 3
（1）Graphene oxide is prepared by improved Hummers method, by 0.7mg graphene oxide and 400mL deionization
Water mixing, the mixture that the two is obtained carry out ultrasonic disperse, and ultrasonic time is 8 h, shine solution with flashlight beam, and do not have
It was found that apparent particle aggregate, illustrates that graphene oxide is well dispersed in aqueous solution, to obtain finely dispersed yellowish-brown
Color graphene oxide dispersion；
（2）At room temperature, by four hydration acetic acid of the 1 of 1g yellowish-brown, 1 '-ferrocenecarboxylic acid powder and 9g pink
Cobalt dust is dissolved in step（1）In resulting graphene oxide dispersion, stirring, until solid all dissolves, solution is by yellowish-brown
Become dark red；
（3）By step（2）Gained brown solution is placed into temperature constant magnetic stirring water-bath, controls constant temperature water bath 50
DEG C, magnetic agitation is opened, sodium hydroxide solution is added dropwise in whipping process（0.5M）, the pH for adjusting solution is 12, is stirred for 10h；
（4）By step（3）Gained system is transferred in water heating kettle, controls temperature at 200 DEG C, hydro-thermal 72h, reaction terminates
Afterwards, reaction solution is taken out from water heating kettle, repeatedly washing centrifugation（Control revolving speed is 8000r/min）, the sediment being centrifuged out is put in
It is dried in 50 DEG C of baking ovens, obtains Co-Fe alloy/graphite alkene composite material precursor；
（5）By step（4）Gained Co-Fe alloy/graphite alkene composite material precursor, is put in agate mortar, carefully grinds
Ground powder is transferred in porcelain boat by 1h, is placed in tube furnace under nitrogen atmosphere, with the heating rate liter of 10 DEG C/min
Temperature is to calcining 8h at 600 DEG C to get Co-Fe alloy/graphite alkene composite material.
Claims (3)
1. a kind of preparation method of Co-Fe alloy/graphite alkene composite material, which is characterized in that steps are as follows：
（1）, by graphene oxide ultrasonic disperse in water；
（2）, at room temperature, by 1,1 '-ferrocenecarboxylic acid and four hydration cobalt acetate stirring and dissolvings in step（1）Resulting oxygen
In graphite alkene dispersion liquid；
（3）, temperature control at 20 ~ 80 DEG C, to step（2）Add alkali in acquired solution while stirring, the pH for adjusting solution is 4 ~ 12, then is stirred
Mix 2 ~ 10 h；
（4）, by step（3）Gained system is transferred in water heating kettle, 40 ~ 200 DEG C of 48 ~ 72h of hydro-thermal, after being cooled to room temperature, is taken out
Reaction solution, isolated sediment, is baked to；
（5）, grinding steps（4）Gained sediment after drying in a nitrogen atmosphere by ground powder is forged at 400 ~ 600 DEG C
2 ~ 8h is burnt to get Co-Fe alloy/graphite alkene composite material；
Wherein, based on mass volume ratio, graphene oxide: water: 1,1 '-ferrocenecarboxylic acid: four hydration cobalt acetate=0.2 ~ 0.7g:
300~400mL∶1g∶1~9g。
2. preparation method as described in claim 1, it is characterised in that：The alkali is sodium hydroxide, is added in the form of its aqueous solution
Enter, the concentration of sodium hydrate aqueous solution is 0.1 ~ 0.5 mol/L.
3. preparation method as described in claim 1, it is characterised in that：It is described to be separated into centrifuge separation, centrifugal rotational speed is 6000 ~
8000r/min。
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| KR101815479B1 (en) * | 2017-07-20 | 2018-01-08 | 한국지질자원연구원 | Manufacturing method of composite containing crumpled grahphene and cobalt-iron oxide, the composite manufactured thereby and supercapacitor containing the composite |
| CN111450862A (en) * | 2020-03-24 | 2020-07-28 | 上海理工大学 | Method for preparing CoFe alloy/graphene oxide/carbon nanotube composite material |
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| CN101710512A (en) * | 2009-11-20 | 2010-05-19 | 哈尔滨工程大学 | Composite material of graphene and carbon-encapsulated ferromagnetic nano metal and preparation method thereof |
| CN103191699A (en) * | 2013-04-23 | 2013-07-10 | 北京化工大学 | Ferrite/graphene composite adsorbent and preparation and using methods thereof |
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| CN101710512A (en) * | 2009-11-20 | 2010-05-19 | 哈尔滨工程大学 | Composite material of graphene and carbon-encapsulated ferromagnetic nano metal and preparation method thereof |
| CN103191699A (en) * | 2013-04-23 | 2013-07-10 | 北京化工大学 | Ferrite/graphene composite adsorbent and preparation and using methods thereof |
| CN103864010A (en) * | 2014-03-05 | 2014-06-18 | 南京理工大学 | Nitrogen-doped graphene/cobalt ferrite nano composite material and preparation method thereof |
| CN105895885A (en) * | 2016-06-17 | 2016-08-24 | 上海应用技术学院 | Method for preparing cobalt ferrite-graphene lithium ion battery by using steel rolling oil sludge |
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