CN102709057A - Method for preparing composite of grapheme with different oxidation degrees and manganese dioxide - Google Patents
Method for preparing composite of grapheme with different oxidation degrees and manganese dioxide Download PDFInfo
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Abstract
The invention discloses a method for preparing composite of grapheme with different oxidation degrees and manganese dioxide. The method comprises the processes of: respectively carrying out low-temperature, intermediate-temperature and high-temperature subsection reactions on original graphite, and concentrated sulfuric acid with a mass concentration of 98% and potassium permanganate so as to obtain graphite oxide; dispersing the graphite oxide in de-ionized water, and reducing the prepared graphite oxide with hydrazine hydrate so as to obtain the grapheme oxide with different oxidation degrees by controlling reduction time; and mixing the grapheme oxide with MnCl2*4H2O in an isopropyl alcohol solution, and adding a water solution of the potassium permanganate to prepare the composite of the grapheme with the different oxidation degrees and the manganese dioxide through oxidation reduction. The method provided by the invention has the advantages as follows: materials used in the method are rich in storage amount and low in cost, so that the method is good in commercialization; an dispersing agent, a stabilizer and the like do not need to be added, and a pure chemical technology is used, so that simple operation, no pollution and low energy consumption can be realized; and the prepared composite material of the grapheme and the manganese dioxide has high purity and good stability.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene and manganese dioxide composites of different degree of oxidations, belong to material with carbon element and metal oxide complex technique.
Background technology
Graphene is a kind of individual layer or the multilayer graphite material as thin as a wafer of discovered in recent years, prepares through the mechanical stripping method from the strong K of the peace moral of Univ Manchester UK in 2004 sea nurse and Constantine Nuo Woxiaoluofu just to have caused global research boom after thickness is about the mono-layer graphite sheet of 1nm and has obtained Nobel prize for physics in 2010.Graphene is to construct sp such as zero dimension fullerene, one dimension CNT, said three-dimensional body phase graphite
2The basic structural unit of hydridization carbon.Graphene has a lot of peculiar performances, and like electric property, mechanical property and the hot property etc. of excellence, its specific area is very big etc. in addition, thereby is with a wide range of applications.
Go deep into gradually along with what Graphene was studied, the research to its derivative at present also becomes focus gradually.Its derivative is considered to grow, the good matrix of loading functional nano material.Graphene oxide is one of important derivatives of Graphene, its surperficial oxygen-containing functional group to nano material its surface position, growth and disperse that very big influence is all arranged.
MnO
2Because of it has the high theoretical specific capacity and characteristics such as reserves are abundant, cheap, chemical property good, environmental friendliness nontoxic pollution-free, be considered to the highly desirable expensive RuO of replacement cost
2The electrochemical capacitance electrode material.The preparation method of Mn oxide has usually: the pyrolysis of the oxidation of manganese metal (manganese metal of electrochemistry or chemical vapour deposition), Mn oxide that the electro-deposition manganese salt solution obtains, manganese compound, sol-gel process etc.But the ratio electric capacity that the resistance of this dvimanganese salt material is very big and high is given the credit to the fake capacitance and the electric transmission speed at electrolyte and reactive species interface place, thereby MnO
2Nanometerization and with the compound focus that has become present research of material with carbon element.At present about the existing report of the compound of preparation manganese dioxide and CNT or Graphene.But do not find Graphene and the preparation of nano-manganese dioxide combination electrode and the application in electrochemical capacitance thereof of research at present about different degree of oxidations.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing different degree of oxidation Graphenes and nano-manganese dioxide composite material, this method has that preparation technology is simple, cost of material is cheap and be suitable for industrialized characteristics.
The present invention realizes that through following technical proposals a kind of Graphene of different degree of oxidations and the preparation method of manganese dioxide composites is characterized in that comprising following process:
1) preparation graphite oxide
It is that to be mixed with concentration in 98% sulfuric acid be 20～35mg/mL sulfuric acid solution that original graphite is added mass fraction, stirs 10min～30min under the condition of ice bath; Keeping temperature to be lower than under 4 ℃ of conditions, is 1 according to original graphite and potassium permanganate mass ratio: (4～6) slowly add potassium permanganate in mixed liquor, and adding finishes continues to stir 90min～120min at ice bath; Be warming up in 32～38 ℃ of water-baths continue to stir 30min～60min after; Be warming up to 57～63 ℃ of insulation 20min～40min again; In mixed liquor, slowly drip deionized water; Cause that the mass concentration of original graphite is reduced to 8～10 mg/mL in the mixed liquor, continue stirring reaction 30min～60min and be cooled to 25～30 ℃, stir and in solution, add deionized water down more rapidly and make in the mixed liquor mass concentration of original graphite reduce to 3～5 mg/mL; Be 1 by hydrogen peroxide solution and mass concentration 98% concentrated sulfuric acid volume ratio again: (3～5); In mixed solution, add hydrogen peroxide solution continuation stirring 30min～60min and finish reaction, obtain removing sulfate ion with mass fraction 10% hydrochloric acid centrifuge washing behind the golden yellow suspension powder that dry down at 60 ℃～80 ℃, grinding obtains graphite oxide;
2) graphene oxide of the different degree of oxidations of preparation
Getting the graphite oxide powder that step 1) makes joins in the deionized water; Sonicated 0.5h～2h obtains the graphite oxide solution that finely dispersed concentration is 0.5～1.5mg/mL; 0.05～0.15 times the hydrazine hydrate that in graphite oxide solution, adds this liquor capacity amount again; Back flow reaction 15min～24h in 77 ℃～83 ℃ water-bath stoves, ultrasonic being scattered in obtains uniform suspension in the deionized water after suction filtration, washing again, and suspension obtains graphene oxide through freeze drying;
3) compound of preparation graphene oxide and nano-manganese dioxide
Press graphene oxide and MnCl
24H
2The O mass ratio is 1: (2～20), and by containing Mn in the solution
2+Concentration is the requirement of 5～30mg/mL, with step 2) preparation graphene oxide powder and MnCl
24H
2O is mixed in the isopropyl alcohol, and ultrasonic 0.5h～2h liquid that is uniformly mixed, mixed solution are 77 ℃～83 ℃ temperature and under stirring; The potassium permanganate solution that in mixed solution, adds 0.1～0.2 times of mixeding liquid volume; Said potassium permanganate solution concentration is 25～35mg/mL, carries out taking out suction filtration behind back flow reaction 20min～40min, and uses the deionized water wash no isopropanol; In 80 ℃ of dryings of temperature, grind the composite powder that obtains graphene oxide and manganese dioxide.
Preparation method of the present invention has the following advantages: the pure chemistry technology is adopted in (1), utilizes the simple oxidation reduction to prepare different degree of oxidation Graphenes and nano-manganese dioxide compound, pollution-free low energy consumption; (2) entire reaction course all is under cryogenic conditions, to accomplish, and is simple to operate; (3) material therefor is reserves and enriches cheap raw material, and cost is low, is beneficial to commercialization; (4) need not to add other materials such as dispersant, stabilizer, the graphene oxide of preparation and nano-manganese dioxide composite material purity are high, and impurity element is few, good stability, and the electrochemical capacitance performance is obvious.
Description of drawings
Fig. 1 is the graphene oxide of one preparation of embodiment among the present invention and the TEM figure of nano-manganese dioxide composite powder.
Fig. 2 is the graphene oxide of four preparations of embodiment among the present invention and the TEM figure of nano-manganese dioxide composite powder.
Fig. 3 is the graphene oxide of six preparations of embodiment among the present invention and the TEM figure of nano-manganese dioxide composite powder.
Fig. 4 is the graphite oxide of one, two, six, eight preparations of embodiment among the present invention and the infrared spectrum of graphene oxide in various degree; Wherein curve (a) is the original graphite oxide of step 1 preparation among the embodiment one, and curve (b), (c), (d), (e) are respectively the graphene oxide powder of step 2 preparation among the embodiment one, two, six, eight.
Fig. 5 is the XRD spectra of the composite powder of two, three, seven preparations of embodiment among the present invention, and wherein curve (a) and (b), (c) are respectively the composite powder of preparation among the embodiment two, three, seven.
The composite powder (75wt%) that Fig. 6 prepares by embodiment among the present invention three, five, seven mixes back preparation electrode and is surveyed charging and discharging curve with conductive black (15wt%) and PTFE (10wt%), wherein curve (a) and (b), (c) are respectively the measured charging and discharging curve of composite powder of preparation among the embodiment three, five, seven.
The composite powder (75wt%) that Fig. 7 prepares by embodiment among the present invention three, five, seven mixes back preparation electrode and is surveyed cyclic voltammetry curve with conductive black (15wt%) and PTFE (10wt%), wherein curve (a) and (b), (c) are respectively the measured cyclic voltammetry curve of composite powder of preparation among the embodiment three, five, seven.
Embodiment
Below in conjunction with embodiment the present invention is further narrated:
Embodiment one:
Step 1: the concentrated sulfuric acid of 120mL mass fraction 98% is poured in the beaker that the original graphite of 3g is housed, stirs 15min under the condition of ice bath; In mixed liquor, slowly add 15gKMnO
4And keep temperature not to be higher than 4 ℃, add the back ice bath that finishes and stir 2h; Mixed liquor moved in 35 ℃ of water-baths be warming up to 60 ℃ of insulation 30min after continuing to stir 1h, in mixed liquor, slowly drip 250mL deionized water control rate of addition and keep system temperature at 60 ± 3 ℃; Adding finishes stirs the 15min taking-up, stirs under the room temperature also to add 500mL deionized water and 30mLH rapidly
2O
2, finish reaction behind the stirring 15min, obtain golden yellow suspension.Remove sulfate ion with 10% watery hydrochloric acid centrifuge washing, 60 ℃ of oven dry 24h grind the powder that obtains GO.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 15min, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains graphene oxide through freeze drying.
Step 3: claim step 2 prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of drying and grinding obtain the 15minGM composite powder, its TEM figure is as shown in Figure 1.The original graphite oxide powder that Fig. 4 (a) and (b) are respectively step 1 preparation and step 2 are reduced the infrared spectrum of the graphene oxide powder for preparing behind the 15min.
Embodiment two:
Step 1: prepare graphite oxide like step 1 among the embodiment one.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 30min, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains the graphene oxide of bigger serface through freeze drying.
Step 3: claim prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of drying and grinding obtain the 30minGM composite powder, its XRD figure spectrum is shown in Fig. 5 (a).The infrared spectrum of the graphene oxide powder that Fig. 4 (c) prepares after for step 2 reduction 30min.
Embodiment three:
Step 1: like embodiment one preparation graphite oxide.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 1h, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains the graphene oxide of bigger serface through freeze drying.
Step 3: claim step 2 prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of dryings, grind and obtain the 1hGM composite powder, its XRD figure is shown in Fig. 5 (b).Fig. 6 (a) mixes back preparation electrode by composite powder (75wt%) and is surveyed charging and discharging curve with conductive black (15wt%) and PTFE (10wt%), Fig. 7 (a) is the cyclic voltammetry curve of electrode.
Embodiment four:
Step 1: like embodiment one preparation graphite oxide.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 2h, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains the graphene oxide of bigger serface through freeze drying.
Step 3: claim step 2 prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of drying and grinding obtain the 2hGM composite powder, its TEM figure is as shown in Figure 2.
Embodiment five:
Step 1: like embodiment one preparation graphite oxide.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 4h, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains the graphene oxide of bigger serface through freeze drying.
Step 3: claim step 2 prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of drying and grinding obtain the 4hGM composite powder.Fig. 6 (b) mixes back preparation electrode by composite powder (75wt%) and is surveyed charging and discharging curve with conductive black (15wt%) and PTFE (10wt%), Fig. 7 (b) is the cyclic voltammetry curve of electrode.
Embodiment six:
Step 1: like embodiment one preparation graphite oxide.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 8h, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains the graphene oxide of bigger serface through freeze drying.
Step 3: claim step 2 prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of drying and grinding obtain the 8hGM composite powder, its TEM figure is as shown in Figure 3.Fig. 4 (d) is the infrared spectrum of the graphene oxide of step 2 preparation.
Embodiment seven:
Step 1: like embodiment one preparation graphite oxide.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 12h, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains the graphene oxide of bigger serface through freeze drying.
Step 3: claim step 2 prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of drying and grinding obtain the 12hGM composite powder, its XRD figure is shown in Fig. 5 (c).Fig. 6 (c) mixes back preparation electrode by composite powder (75wt%) and is surveyed charging and discharging curve with conductive black (15wt%) and PTFE (10wt%), Fig. 7 (c) is the cyclic voltammetry curve of electrode.
Embodiment eight:
Step 1: like embodiment one preparation graphite oxide.
Step 2: the GO powder 0.1g that gets the step 1 preparation joins in the 100mL deionized water; Sonicated 2h obtains finely dispersed 1mg/mL graphite oxide solution; Solution is transferred in the round-bottomed flask and adds to be put in 80 ℃ of water-bath stoves after 100 μ L hydrazine hydrates shake up reflux; Control recovery time 24h, ultrasonic again being scattered in obtains uniform suspension after taking-up back suction filtration, the washing in the deionized water, obtains the graphene oxide of bigger serface through freeze drying.
Step 3: claim step 2 prepared graphene oxide powder 0.066g and MnCl
24H
2O (0.27g) is mixed in ultrasonic 2h in the 50mL isopropyl alcohol, places 80 ℃ of water-baths to stir scattered mixed solution, is dissolved with 0.15gKMnO to wherein pouring 5mL rapidly into
4Deionized water, take out suction filtration, washing behind the backflow 30min, 80 ℃ of drying and grinding obtain the 24hGM composite powder.Fig. 4 (e) is the infrared spectrum of the graphene oxide for preparing behind the step 2 reductase 12 4h.
Claims (1)
1. the preparation method of the Graphene of different degree of oxidations and manganese dioxide composites is characterized in that comprising following process:
1) preparation graphite oxide
It is that to be mixed with concentration in 98% sulfuric acid be 20～35mg/mL sulfuric acid solution that original graphite is added mass fraction, stirs 10min～30min under the condition of ice bath; Keeping temperature to be lower than under 4 ℃ of conditions, is 1 according to original graphite and potassium permanganate mass ratio: (4～6) slowly add potassium permanganate in mixed liquor, and adding finishes continues to stir 90min～120min at ice bath; Be warming up in 32～38 ℃ of water-baths continue to stir 30min～60min after; Be warming up to 57～63 ℃ of insulation 20min～40min again; In mixed liquor, slowly drip deionized water; Cause that the mass concentration of original graphite is reduced to 8～10mg/mL in the mixed liquor, continue stirring reaction 30min～60min and be cooled to 25～30 ℃, stir and in solution, add deionized water down more rapidly and make in the mixed liquor mass concentration of original graphite reduce to 3～5mg/mL; Be 1 by hydrogen peroxide solution and mass concentration 98% concentrated sulfuric acid volume ratio again: (3～5); In mixed solution, add hydrogen peroxide solution continuation stirring 30min～60min and finish reaction, obtain removing sulfate ion with mass fraction 10% hydrochloric acid centrifuge washing behind the golden yellow suspension powder that dry down at 60 ℃～80 ℃, grinding obtains graphite oxide;
2) graphene oxide of the different degree of oxidations of preparation
Getting the graphite oxide powder that step 1) makes joins in the deionized water; Sonicated 0.5h～2h obtains the graphite oxide solution that finely dispersed concentration is 0.5～1.5mg/mL; 0.05～0.15 times the hydrazine hydrate that in graphite oxide solution, adds this liquor capacity amount again; Back flow reaction 15min～24h in 77～83 ℃ of water-bath stoves, ultrasonic being scattered in obtains uniform suspension in the deionized water after suction filtration, washing again, and suspension obtains graphene oxide through freeze drying;
3) compound of preparation graphene oxide and nano-manganese dioxide
Press graphene oxide and MnCl
24H
2The O mass ratio is 1: (2～20), and by containing Mn in the solution
2+Concentration is the requirement of 5～30mg/mL, with step 2) preparation graphene oxide powder and MnCl
24H
2O is mixed in the isopropyl alcohol, and ultrasonic 0.5h～2h liquid that is uniformly mixed, mixed solution are 77～83 ℃ of temperature and under stirring; The potassium permanganate solution that in mixed solution, adds 0.1～0.2 times of mixeding liquid volume; Said potassium permanganate solution concentration is 25～35mg/mL, carries out taking out suction filtration behind back flow reaction 20min～40min, and uses the deionized water wash no isopropanol; In 80 ℃ of dryings of temperature, grind the composite powder that obtains graphene oxide and manganese dioxide.
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| CN106311130A (en) * | 2016-09-13 | 2017-01-11 | 哈尔滨工程大学 | Modified attapulgite material and its preparation and application methods |
| CN106946245A (en) * | 2017-03-20 | 2017-07-14 | 上海大学 | A kind of preparation method of needle-like manganese dioxide/graphene oxide composite nano materials |
| CN107761195A (en) * | 2017-10-26 | 2018-03-06 | 青岛大学 | A kind of lignin-base nano carbon fibre preparation method for electrode of super capacitor |
| CN111477467A (en) * | 2019-01-23 | 2020-07-31 | 哈尔滨工业大学（深圳） | Method for rapidly preparing graphene oxide and manganese oxide composite material |
| CN110610817A (en) * | 2019-10-09 | 2019-12-24 | 浙江天能能源科技股份有限公司 | Based on Mn3O4Supercapacitor made of graphene composite material and preparation method of supercapacitor |
| CN113571345A (en) * | 2021-06-30 | 2021-10-29 | 哈尔滨工程大学 | Preparation process method of manganese dioxide doped graphene oxide electrode film |
| CN115155546A (en) * | 2022-07-07 | 2022-10-11 | 中国人民解放***箭军工程大学 | Graphene oxide, preparation method thereof, method for adsorbing unsymmetrical dimethylhydrazine in aqueous solution by using graphene oxide and application of graphene oxide |
| CN115155546B (en) * | 2022-07-07 | 2023-11-21 | 中国人民解放***箭军工程大学 | Graphene oxide and preparation method thereof, and method and application for adsorbing unsymmetrical dimethylhydrazine in aqueous solution by using graphene oxide |
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