CN106128802B - A kind of preparation method for the electrode material of supercapacitor - Google Patents

Abstract

A kind of preparation method of electrode material for ultracapacitor of the invention, stannic oxide/graphene nano band ultrasonic disperse is obtained into stannic oxide/graphene nano band dispersion liquid in water；Aniline is added into graphene oxide band aqueous dispersion, initiator is added after stirring, the mixed dispersion liquid of intermediate product is obtained after reaction；Manganese dioxide nano particle is added in the mixed dispersion liquid of intermediate product, then ultrasonic disperse obtains the mixed dispersion liquid of manganese dioxide nano particle/intermediate product；Aniline is continuously added into the mixed dispersion liquid of manganese dioxide nano particle/intermediate product, stirring reaction, filtering, is washed to pH value neutrality, the electrode material that graphene nanobelt/manganese dioxide/polyaniline is used for ultracapacitor is obtained after drying.When graphene nanobelt/manganese dioxide/the polyaniline composite material being prepared by the method for the present invention is used as electrochemical capacitance electrode material, excellent capacitive property and cycle life are shown.

Description

A kind of preparation method for the electrode material of supercapacitor

technical field

The invention belongs to the field of physics and relates to an electrode material, in particular to a method for preparing an electrode material for a supercapacitor.

Background technique

Supercapacitor is an energy storage device between ordinary capacitors and chemical batteries, which has the advantages of both, such as high power density, high energy density, long cycle life, fast charge and discharge, and instantaneous high current discharge And the characteristics of no pollution to the environment. Because of its extremely important and broad application prospects, it has become one of the research hotspots. As a new type of energy storage device with green environmental protection and excellent performance, supercapacitors are widely used in many fields. Electrolyte materials are the key factors affecting the performance of supercapacitors. Therefore, in recent years, people have made a lot of research on the preparation, synthesis and modification of supercapacitor materials.

Manganese dioxide is an ideal supercapacitor material, because manganese dioxide has many advantages as a supercapacitor material: high theoretical capacitance value, good environmental compatibility, low price, non-toxic and safe, and abundant reserves. However, in practical applications, the performance of pure-phase manganese dioxide is often not high due to its poor conductivity and the electrochemical dissolution of the manganese dioxide electrode that occurs during cycling. Therefore, the pure phase of manganese dioxide still has many deficiencies as a supercapacitor material. Graphene nanobelt is a new type of material after carbon nanotubes and graphene nanosheets. Its excellent mechanical and electrochemical properties make it a good material for electrochemical and some electronic devices, such as lithium-ion batteries. , supercapacitors, etc. At present, the use of carbon materials and conductive polymers to modify manganese dioxide has become one of the research hotspots of researchers in the field.

Li et al. have synthesized a composite material of multi-walled carbon nanotube/polyaniline/manganese dioxide, and the electrochemical performance of the obtained composite material has been greatly improved (LiQ, LiuJ, ZouJ, et al.Synthesisandelectrochemicalperformanceofmulti-walledcarbonnanotube/polyaniline /MnO ₂ ternarycoaxialnanostructuresforsupercapacitors[J].JournalofPowerSources2011,196(1):565-572). Jena et al obtained a composite material by functionalizing multi-walled carbon nanotubes with polyaniline and manganese dioxide, and the composite material has excellent performance (SkMM, _YueCY , JenaRK. ) [J]. Synthetic Metals 2015, 208: 2-12.). Wang et al. synthesized sulfonated graphene/polyaniline/manganese dioxide composite material, and the obtained material has good rate performance and stable cycle performance (WangG, TangQ, BaoH, LiX, et al.Synthesisofhierarchicalsulfonatedgraphene/MnO ₂ /polyanilineternarycompositeanditsimprovedelectrochemicalperformance[ J]. Journal of Power Sources 2013, 241:231-238.). Therefore, the synthesis of composite materials has a significant effect on improving manganese dioxide supercapacitor materials.

purpose of invention

Aiming at the above-mentioned technical problems in the prior art, the present invention provides a method for preparing an electrode material for a supercapacitor. The method for preparing an electrode material for a supercapacitor should solve the two problems in the prior art. The poor conductivity of the manganese oxide electrode material and the electrochemical dissolution of the electrode during the cycle lead to the technical problems of its poor performance in practical applications.

The invention provides a kind of preparation method for the electrode material of supercapacitor, comprises the steps:

1) ultrasonically dispersing the graphene oxide nanobelts in water to obtain a graphene oxide nanobelt dispersion, the mass dispersion concentration of the graphene oxide nanobelts in water is 0.1 to 10 mg/mL;

2) Add the first batch of aniline to the graphene oxide ribbon dispersion solution prepared in step 1), the mass ratio of the first batch of aniline to graphene oxide nanobelts is 0.1 to 20:1, and stir for 5 to 30 minutes , followed by adding an initiator, the mass ratio of the initiator to the graphene oxide nanobelt is 0.1 to 25:1 at -10 to 5°C, stirring and reacting for 5 to 60 minutes to obtain a mixed dispersion of the intermediate product;

3) Weigh manganese dioxide nanoparticles and add them to the mixed dispersion of the intermediate product obtained in step 2), the mass ratio of the manganese dioxide nanoparticles and graphene oxide nanobelts is 0.1 to 15:1, and then ultrasonically Disperse for 5 to 60 minutes to obtain a mixed dispersion of manganese dioxide nanoparticles/intermediate product;

4) continue to add the second batch of aniline in the mixed dispersion liquid that makes manganese dioxide nanoparticles/intermediate product in step 3), the mass ratio of described second batch of aniline and graphene oxide nanobelt is 0.1～20: 1. Stir and react at -10-5°C for 5-60 minutes, filter, and wash repeatedly with ethanol and deionized water until the pH value is neutral, and dry the obtained material at 60-80°C for 24-48 hours. That is, the graphene nanobelt/manganese dioxide/polyaniline is obtained as an electrode material for a supercapacitor.

Further, in the step 2), the initiator is hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, potassium dichromate, sodium dichromate, ferric chloride, or manganese chloride any one or a combination of two or more.

Further, in the step 3), the manganese dioxide nanoparticles are any one or both of manganese dioxide nanowires, manganese dioxide nanosheets, manganese dioxide nanorods, or manganese dioxide nanospheres. more than one combination.

The invention adopts a simple in-situ polymerization method to realize the effective compounding of graphene nanobelt/manganese dioxide/polyaniline. Firstly, the aniline solution is first added to the water dispersion of graphene nanobelt, and then the initiator is added. After in-situ polymerization for a certain period of time, a certain amount of manganese dioxide nanoparticles and aniline solution are sequentially added, and further in-situ polymerization is performed to obtain a graphene nanoribbon/manganese dioxide/polyaniline composite material. When the graphene nanobelt/manganese dioxide/polyaniline composite material prepared by the method of the invention is used as a supercapacitor electrode material, it exhibits excellent capacitance performance and cycle life, and is applicable to water and organic solution electrolyte systems.

The synthesis method of the present invention adopts the method of hydrothermal combination in-situ polymerization, the method is simple and easy, the energy consumption is small and the environment is friendly, and the supercapacitor electrode material is easy to achieve large-scale preparation for industrial production. The supercapacitor electrode material provided by the invention has a large specific surface area, a network structure and good conductivity. By combining metal oxides with graphene and its derivative materials and conductive polymers, through the synergistic effect between each other, the shortcoming of poor conductivity of pure manganese dioxide has been successfully improved. The electrode material of the present invention is made into a supercapacitor pole piece, and tested in a neutral electrolyte by a three-electrode system, wherein the supercapacitor pole piece is composed of: 80 parts of synthetic ternary supercapacitor active materials, 10 parts of Conductive agent, 10 parts of binder. Tests show that the electrode material of the invention has good performance, high specific capacitance value, good rate performance and good cycle stability.

Compared with the prior art, the technical progress of the present invention is remarkable. The invention obtains the graphene nanobelt/manganese dioxide/polyaniline as an electrode material for a supercapacitor by compounding the novel material graphene nanobelt, polyaniline and manganese dioxide, and combining hydrothermal in-situ polymerization. The obtained composite material has good cycle performance and high specific capacitance, is an ideal supercapacitor electrode material, and is suitable for industrial production.

Description of drawings

Fig. 1 is the SEM image of the graphene nanobelt/manganese dioxide/polyaniline ternary supercapacitor electrode material prepared in Example 1 of the present invention.

Fig. 2 is a charge-discharge curve diagram of the graphene nanobelt/manganese dioxide/polyaniline ternary supercapacitor electrode material prepared in Example 1 of the present invention.

Fig. 3 is the cyclic voltammogram of the graphene nanobelt/manganese dioxide/polyaniline ternary supercapacitor electrode material prepared in Example 1 of the present invention.

Fig. 4 is a cycle stability diagram of the graphene nanobelt/manganese dioxide/polyaniline ternary supercapacitor electrode material prepared in Example 1 of the present invention.

detailed description

Example 1

(1) Ultrasonic dispersion of 100mg graphene oxide nanoribbon in 100ml water obtains the graphene oxide nanoribbon dispersion liquid of 1mg/mL;

(2) To the graphene oxide band dispersion aqueous solution that step (1) makes, add the aniline of 0.1g (the mass ratio of aniline and graphene nanoribbon is 1:1), stir 15 minutes, then add the persulfuric acid of 0.2g Ammonium, (the mass ratio of ammonium persulfate to graphene nanobelts is 2:1), at -5°C, stirred and reacted for 15 minutes to obtain a mixed dispersion of the intermediate product;

(3) Weigh the manganese dioxide nanorods of 0.6g (the mass ratio of manganese dioxide nanorods and graphene nanobelts is 6:1), join in the mixed dispersion liquid of the intermediate product that step (2) obtains and ultrasonic Disperse for 10 minutes to obtain a mixed dispersion of manganese dioxide nanorods/intermediate product;

(4) Continue to add the aniline of 0.1g (the mass ratio of aniline and graphene nanoribbon is 1:1) in the mixed dispersion liquid of manganese dioxide nanorod/intermediate product obtained in step (3), at-2 ℃ , stirred and reacted for 50 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and dried at 70°C for 24 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline. electrode materials for supercapacitors.

Wherein, Fig. 1 is the SEM figure of example 1, it can be seen that the electrode material for supercapacitor synthesized in example 1 presents a porous network structure in the figure, and polyaniline nanoparticles are successfully loaded on manganese dioxide nanorods and graphene nanoribbons superior. Fig. 2 is the galvanostatic charge-discharge diagram under the condition of 1,2,5,10A/g of the ternary supercapacitor electrode material synthesized in example 1, it can be seen that the charge-discharge curves can all be obtained under different current densities The symmetry is maintained, indicating its good Coulombic efficiency. Figure 3 is the cyclic voltammogram of the ternary supercapacitor material synthesized in Example 1 under the conditions of 5, 10, 20, and 50mv/s. It can be seen that the ternary supercapacitor material can maintain The rectangular-like shape indicates its good capacitive properties. Figure 4 is a cycle performance diagram of the ternary supercapacitor material synthesized by the example at a current density of 1A/g. After 1000 cycles of charging and discharging, the capacitance retention rate is about 85%, indicating that it has a good cycle as a supercapacitor material performance.

Example 2

(1) 500mg graphene oxide nanobelts are ultrasonically dispersed in 100ml water to obtain a 5mg/mL graphene oxide nanobelt dispersion;

(2) Add 0.25g of aniline (the mass ratio of aniline to graphene nanoribbon is 0.5:1) to the graphene oxide ribbon dispersion solution prepared in step (1), stir for 20 minutes, then add 0.5g of chlorinated Iron (mass ratio of ferric chloride to graphene nanobelts is 1:1), at -5°C, stirred and reacted for 20 minutes to obtain a mixed dispersion of the intermediate product;

(3) Weigh 1g of manganese dioxide nanorods (the mass ratio of manganese dioxide nanorods and graphene nanobelts is 2:1), join the mixed dispersion liquid of the intermediate product obtained in step (2) and ultrasonically disperse Obtain the mixed dispersion liquid of manganese dioxide nanorod/intermediate product in 15 minutes;

(4) continue to add the aniline of 0.25g (the mass ratio of aniline and graphene nanoribbon is 0.5:1) in the mixed dispersion liquid that makes manganese dioxide nanorod/intermediate product in step (3), at 0 ℃ , stirred and reacted for 40 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and the resulting material was dried at 75°C for 30 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline for use in Electrode materials for supercapacitors.

Example 3

(1) Ultrasonic dispersion of 200mg graphene oxide nanoribbon in 100ml water obtains the graphene oxide nanoribbon dispersion liquid of 2mg/mL;

(2) to the graphene oxide band dispersion aqueous solution that step (1) makes, add the aniline of 0.4g (the mass ratio of aniline and graphene nanoribbon is 2:1), stir 15 minutes, then add the persulfuric acid of 0.6g Sodium (the mass ratio of sodium persulfate to graphene nanobelts is 3:1), at -5°C, stirred and reacted for 20 minutes to obtain a mixed dispersion of the intermediate product;

(3) Weigh the manganese dioxide nanosheets of 0.8g (the mass ratio of manganese dioxide nanosheets and graphene nanobelts is 4:1), join in the mixed dispersion liquid of the intermediate product that step (2) obtains and then ultrasonic Disperse for 30 minutes to obtain a mixed dispersion of manganese dioxide nanosheets/intermediate product;

(4) continue to add the aniline of 0.4g (the mass ratio of aniline and graphene nanoribbon is 2:1) in the mixed dispersion liquid that makes manganese dioxide nanosheet/intermediate product in step (3), at-2 ℃ , stirred and reacted for 30 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and dried at 70°C for 30 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline. electrode materials for supercapacitors.

Example 4

(1) 300mg graphene oxide nanobelts are ultrasonically dispersed in 100ml water to obtain a 3mg/mL graphene oxide nanobelt dispersion;

(2) Add 0.9 g of aniline (the mass ratio of aniline and graphene nanoribbons to 3:1) to the graphene oxide ribbon dispersion solution prepared in step (1), stir for 20 minutes, then add 1.2 g of peroxide Hydrogen (the mass ratio of hydrogen peroxide and graphene nanobelts is 4:1), at -2°C, stirred and reacted for 20 minutes to obtain a mixed dispersion of the intermediate product;

(3) Weigh the manganese dioxide nanosheets of 0.15g (the mass ratio of manganese dioxide nanosheets and graphene nanobelts is 0.5:1), join in the mixed dispersion liquid of the intermediate product that step (2) obtains and then ultrasonic Disperse for 20 minutes to obtain a mixed dispersion of manganese dioxide nanosheets/intermediate product;

(4) continue to add the aniline of 0.9g (the mass ratio of aniline and graphene nanoribbon is 3:1) in the mixed dispersion liquid that makes manganese dioxide nanosheet/intermediate product in step (3), at-1 ℃ , stirred and reacted for 60 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and dried at 80°C for 36 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline. electrode materials for supercapacitors.

Example 5

(1) Ultrasonic dispersion of 600mg graphene oxide nanoribbon in 100ml water obtains the graphene oxide nanoribbon dispersion liquid of 6mg/mL;

(2) to the graphene oxide band dispersion aqueous solution that step (1) makes, add the aniline of 2.4g (the mass ratio of aniline and graphene nanoribbon is 4:1), stir 15 minutes, then add the persulfuric acid of 1.2g Ammonium (the mass ratio of ammonium persulfate to graphene nanobelts is 2:1), at -5°C, stirred and reacted for 15 minutes to obtain a mixed dispersion of the intermediate product;

(3) Weigh the manganese dioxide nanowires of 1.8g (the mass ratio of manganese dioxide nanowires and graphene nanobelts is 3:1), add it to the mixed dispersion of the intermediate product obtained in step (2) and then ultrasonically Disperse for 10 minutes to obtain a mixed dispersion of manganese dioxide nanowires/intermediate product;

(4) Continue to add 2.4g of aniline (the mass ratio of aniline and graphene nanoribbon is 4:1) in the mixed dispersion liquid of manganese dioxide nanowire/intermediate product obtained in step (3), at-2 ℃ , stirred and reacted for 40 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and dried at 70°C for 28 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline. electrode materials for supercapacitors.

Example 6

(1) Ultrasonic dispersion of 800mg graphene oxide nanoribbon in 100ml water obtains the graphene oxide nanoribbon dispersion liquid of 8mg/mL;

(2) Add 0.4g of aniline (the mass ratio of aniline to graphene nanoribbons is 0.5:1) to the graphene oxide ribbon dispersion solution prepared in step (1), stir for 30 minutes, then add 1.6g of peroxide Hydrogen (the mass ratio of hydrogen peroxide to graphene nanobelts is 2:1), at -5°C, stirred and reacted for 30 minutes to obtain a mixed dispersion of the intermediate product;

(3) Weigh the manganese dioxide nanospheres of 1.6g (the mass ratio of manganese dioxide nanospheres and graphene nanobelts is 2:1), join in the mixed dispersion liquid of the intermediate product that step (2) obtains and then ultrasonic Disperse for 15 minutes to obtain a mixed dispersion of manganese dioxide nanospheres/intermediate product;

(4) continue to add the aniline of 0.4g (the mass ratio of aniline and graphene nanobelt is 0.5:1) in the mixed dispersion liquid that makes manganese dioxide nanosphere/intermediate product in step (3), at-2 ℃ , stirred and reacted for 60 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and dried at 80°C for 48 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline. electrode materials for supercapacitors.

Example 7

(1) 200mg graphene oxide nanobelts are ultrasonically dispersed in 100ml water to obtain a 2mg/mL graphene oxide nanobelt dispersion;

(2) to the graphene oxide band dispersion aqueous solution that step (1) makes, add the aniline of 1g (the mass ratio of aniline and graphene nanoribbon is 5:1), stir 15 minutes, then add the ammonium persulfate of 0.8g (the mass ratio of ammonium persulfate to graphene nanoribbon is 4:1), at -5 ℃, stirred and reacted for 30 minutes to obtain the mixed dispersion liquid of the intermediate product;

(3) Weigh the manganese dioxide nanowires of 0.2g (the mass ratio of manganese dioxide nanowires and graphene nanobelts is 1:1), add it to the mixed dispersion of the intermediate product obtained in step (2) and ultrasonically Disperse for 15 minutes to obtain a mixed dispersion of manganese dioxide nanowires/intermediate product;

(4) Continue to add 1g of aniline (the mass ratio of aniline and graphene nanoribbon is 5:1) in the mixed dispersion liquid of manganese dioxide nanowire/intermediate product obtained in step (3), at -2 ℃ , stirred and reacted for 40 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and the resulting material was dried at 70°C for 32 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline for use in Electrode materials for supercapacitors.

Example 8

(1) 50mg graphene oxide nanobelts are ultrasonically dispersed in 100ml water to obtain a 0.5mg/mL graphene oxide nanobelt dispersion;

(2) To the graphene oxide band dispersion aqueous solution that step (1) makes, add the aniline of 0.3g (the mass ratio of aniline and graphene nanoribbon is 6:1), stir 15 minutes, then add the chlorinated 0.4g Manganese (the mass ratio of manganese chloride to graphene nanobelts is 8:1), at -5°C, stirred and reacted for 20 minutes to obtain a mixed dispersion of the intermediate product;

(3) Weigh the manganese dioxide nanosheets of 0.4g (the mass ratio of manganese dioxide nanosheets and graphene nanobelts is 8:1), join in the mixed dispersion liquid of the intermediate product that step (2) obtains and then ultrasonic Disperse for 20 minutes to obtain a mixed dispersion of manganese dioxide nanosheets/intermediate product;

(4) continue to add the aniline of 0.3g (the mass ratio of aniline and graphene nanobelt is 6:1) in the mixed dispersion liquid that makes manganese dioxide nanosheet/intermediate product in step (3), at-2 ℃ , stirred and reacted for 30 minutes, filtered, and repeatedly washed with ethanol and deionized water until the pH value was neutral, and dried at 70°C for 24 hours to obtain graphene nanoribbons/manganese dioxide/polyaniline. electrode materials for supercapacitors.

Claims (3)

1. the preparation method of a kind of electrode material for ultracapacitor, it is characterised in that comprise the following steps：

1) stannic oxide/graphene nano band ultrasonic disperse is obtained into stannic oxide/graphene nano band dispersion liquid, described oxidation stone in water Mass-dispersion concentration of the black alkene nanobelt in water is 0.1~10mg/mL；

2) add first aniline into stannic oxide/graphene nano band dispersion liquid made from step 1), first described aniline with The mass ratio of stannic oxide/graphene nano band is 0.1~20:1, stir 5~30 minutes, then add initiator, described initiator Mass ratio with stannic oxide/graphene nano band is 0.1~25:1, at -10~5 DEG C, stirring reaction obtains centre in 5~60 minutes The mixed dispersion liquid of product；

3) manganese dioxide nano particle is weighed, is added in the mixed dispersion liquid for the intermediate product that step 2) obtains, described two The mass ratio of manganese oxide nano granule and stannic oxide/graphene nano band is 0.1~15：1, then ultrasonic disperse 5~60 minutes, are obtained To the mixed dispersion liquid of manganese dioxide nano particle/intermediate product；

4) it is made into step 3) in the mixed dispersion liquid of manganese dioxide nano particle/intermediate product and continuously adds second batch benzene The mass ratio of amine, described second batch aniline and stannic oxide/graphene nano band is 0.1~20:1, at -10~5 DEG C, stirring is anti- Answer 5~60 minutes, filter, and it is neutral to pH value with ethanol, deionized water repeated washing successively, by the material of gained 60~80 DEG C dry 24~48 hours, that is, obtain graphene nanobelt/manganese dioxide/polyaniline be used for ultracapacitor electrode material.

A kind of 2. preparation method of electrode material for ultracapacitor according to claim 1, it is characterised in that：Institute State in step 2), described initiator is hydrogen peroxide, potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, potassium bichromate, dichromic acid Any one in sodium, iron chloride or manganese chloride or two or more combinations.

A kind of 3. preparation method of electrode material for ultracapacitor according to claim 1, it is characterised in that：Institute State in step 3), described manganese dioxide nano particle is manganese dioxide nanowire, manganese dioxide nano-plates, manganese dioxide nano Any one in rod or manganese dioxide nano ball or two or more combinations.