CN106409524B - Supercapacitor graphene/LaMnO3 composite material preparation method - Google Patents

Supercapacitor graphene/LaMnO3 composite material preparation method Download PDF

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CN106409524B
CN106409524B CN201611091388.6A CN201611091388A CN106409524B CN 106409524 B CN106409524 B CN 106409524B CN 201611091388 A CN201611091388 A CN 201611091388A CN 106409524 B CN106409524 B CN 106409524B
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graphene
solution
composite material
lamno
supercapacitor
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CN106409524A (en
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王耀
金利华
冯建情
李成山
张平祥
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Northwest Institute for Non Ferrous Metal Research
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    • Y02E60/13—Energy storage using capacitors

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Abstract

The present invention provides a kind of supercapacitor graphene/LaMnO3The preparation method of composite material, comprising the following steps: one, by graphene oxide ultrasonic disperse in dehydrated alcohol, obtain solution A；Two, lanthanum acetylacetone and manganese acetylacetonate are dissolved in propionic acid, obtain solution B；Three, solution A and solution B are uniformly mixed, are then added to progress rotary evaporation processing in Rotary Evaporators, obtain the precursor C that form is gel state；Four, precursor C is subjected under the protection of reducibility gas high-temperature heat treatment, obtains supercapacitor graphene/LaMnO3Composite material.Preparation process of the present invention is simple, at low cost, prepared graphene/LaMnO3Composite material specific capacitance with higher and preferable cyclical stability, and be suitable for being mass produced.

Description

Supercapacitor graphene/LaMnO3The preparation method of composite material
Technical field
The invention belongs to electrode material for super capacitor technical fields, and in particular to a kind of supercapacitor with graphene/ LaMnO3The preparation method of composite material.
Background technique
In order to solve the problems, such as energy crisis and environmental pollution that human society is faced, people are attempting always exploitation ring The new energy of border close friend.The novel energy storage apparatus supercapacitor developed in recent years due to have the advantages that it is a series of and by People's concern, not only power density is high, the service life is long for it, wide using temperature, but also it is also very fast to charge.For supercapacitor For, the quality good or not of electrode material is the key factor for determining its performance.People are exploring always as simple as possible Method obtains high performance electrode material.Since graphene discovery, the application in supercapacitor field just receives people Extensive concern.Especially in recent years it has been developed that a large amount of graphene composite material, including graphene/inorganic compounding The graphene-based composite material of material, grapheme/electroconductive polymer composite and ternary, these composite materials are widely answered Used in supercapacitor.
Perovskite manganites LaMnO3System is since the particularity of structure and magnetic electricity performance etc. is to solid Fluid fuel battery, solid electrolyte and catalysis aspect have been obtained and are widely applied, and equally, people have attempted in recent years The LaMnO as electrode material for super capacitor is prepared3Active material, however often introduce in the synthesis process some non- The harmful substance of environmental protection, and its specific capacity is all relatively relatively low.Therefore, from practical angle, there is an urgent need to low cost Technology path is that approach solves the problems, such as prepared by electrode material for super capacitor by optimization technique.
It is found that inorganic material, which is distributed to graphene nanometer sheet surface, is made graphene/inorganic nano composite material, It can not only inhibit to reunite between graphene sheet layer, but also the intrinsic of graphene and inorganic nano-particle can be kept simultaneously Characteristic, or even synergistic effect can be generated, therefore be with a wide range of applications.Therefore using the chemical method route system of low cost Standby graphene/LaMnO3Composite material is very important realization electrode material for super capacitor low-cost technologies route, It is of great significance simultaneously for the progress of Preparation Technology of promotion supercapacitor.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of supercapacitor With graphene/LaMnO3The preparation method of composite material.This method simple process, at low cost, made graphene/LaMnO3It is compound Material specific capacitance with higher and preferable cyclical stability, and be suitable for being mass produced.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of supercapacitor with graphene/ LaMnO3The preparation method of composite material, which is characterized in that method includes the following steps:
Step 1: graphene oxide ultrasonic disperse is obtained solution A in dehydrated alcohol；
Step 2: lanthanum acetylacetone and manganese acetylacetonate are after mixing dissolved in propionic acid at 1: 1 in molar ratio, obtain Solution B；
Step 3: by solution B described in solution A described in step 1 and step 2 by volume 1: (1~3) mixes equal It is even, it is then added to progress rotary evaporation processing in Rotary Evaporators, obtains the precursor C that form is gel state；
Step 4: precursor C described in step 3 is carried out high-temperature heat treatment under the protection of reducibility gas, surpassed Grade capacitor graphene/LaMnO3Composite material；The detailed process of the high-temperature heat treatment are as follows: first with 5 DEG C/min~200 DEG C/heating rate of min keeps the temperature 1h~3h after being warming up to 900 DEG C~1100 DEG C, then with 2 DEG C/min~10 DEG C/min cooling Rate is down to 25 DEG C of room temperatures.
Above-mentioned supercapacitor graphene/LaMnO3The preparation method of composite material, which is characterized in that in step 1 The concentration of graphene oxide is 1mg/mL~5mg/mL in the solution A.
Above-mentioned supercapacitor graphene/LaMnO3The preparation method of composite material, which is characterized in that in step 2 The total concentration of metal cation is 0.1mol/L~0.8mol/L in the solution B.
Above-mentioned supercapacitor graphene/LaMnO3The preparation method of composite material, which is characterized in that in step 3 The temperature of the rotary evaporation processing is 70 DEG C~100 DEG C, and the time of the rotary evaporation processing is 30min~60min.
Above-mentioned supercapacitor graphene/LaMnO3The preparation method of composite material, which is characterized in that in step 4 The reducibility gas is argon hydrogen mixture or nitrogen hydrogen mixeding gas, hydrogen in the argon hydrogen mixture and nitrogen hydrogen mixeding gas The volumn concentration of gas is 4%~5%.
Compared with the prior art, the present invention has the following advantages:
1, preparation method of the present invention is simple, using conventional raw material, does not need special installation, preparation cost is low.
2, the present invention can be in atmosphere gas to atmosphere without strict demand using conventional simple metal organic salt preparation precursor liquid Precursor liquid is prepared in atmosphere, effectively improves the stability of precursor liquid, simplifies the preparation process of precursor liquid.
3, the present invention directly adopt solvent evaporated method obtain gel, using one-step method be heat-treated be made graphene/ LaMnO3Composite material, preparation process is simple, and graphene/LaMnO may be implemented3The low cost of composite material, large-scale production.
4, the graphene/LaMnO prepared using method of the invention3Composite material specific capacitance with higher and preferable Cyclical stability, and more single LaMnO3The chemical property of active material is significantly improved.
Invention is further described in detail with reference to the accompanying drawings and examples.
Detailed description of the invention
Fig. 1 is graphene/LaMnO prepared by the embodiment of the present invention 13The cycle life curve of composite material.
Specific embodiment
Embodiment 1
The present embodiment supercapacitor graphene/LaMnO3The preparation method of composite material the following steps are included:
Step 1: graphene oxide ultrasonic disperse is obtained solution A in dehydrated alcohol；Graphite oxide in the solution A The concentration of alkene is 1mg/mL；
Step 2: by lanthanum acetylacetone and manganese acetylacetonate in molar ratio 1: 1 be uniformly mixed and be dissolved in propionic acid, obtain Solution B；The total concentration of metal cation is 0.1mol/L in the solution B；
Step 3: solution B described in solution A described in step 1 and step 2 is uniformly mixed at 1: 1 by volume, so After be added in Rotary Evaporators progress rotary evaporation processing, obtain the precursor C that form is gel state；At the rotary evaporation The temperature of reason is 70 DEG C, and the time of the rotary evaporation processing is 60min；
Step 4: precursor C described in step 3 is carried out high-temperature heat treatment under the protection of reducibility gas, surpassed Grade capacitor graphene/LaMnO3Composite material；The reducibility gas is argon hydrogen mixture, the argon hydrogen mixture The volumn concentration of middle hydrogen is 4%, the detailed process of the high-temperature heat treatment are as follows: first with the heating rate of 200 DEG C/min 1h is kept the temperature after being warming up to 1100 DEG C, and 25 DEG C of room temperatures are then down to the rate of temperature fall of 2 DEG C/min.
To supercapacitor manufactured in the present embodiment graphene/LaMnO3Composite material carries out charge-discharge test, follows For ring life curve as shown in Figure 1, under the conditions of current density is 0.5A/g, specific capacity value has reached 259F/g；By 1000 Specific capacity remains at 96% or more after secondary charge-discharge test.
Embodiment 2
The present embodiment supercapacitor graphene/LaMnO3The preparation method of composite material the following steps are included:
Step 1: graphene oxide ultrasonic disperse is obtained solution A in dehydrated alcohol；Graphite oxide in the solution A The concentration of alkene is 3mg/mL；
Step 2: by lanthanum acetylacetone and manganese acetylacetonate in molar ratio 1: 1 be uniformly mixed and be dissolved in propionic acid, obtain Solution B；The total concentration of metal cation is 0.4mol/L in the solution B；
Step 3: solution B described in solution A described in step 1 and step 2 is uniformly mixed at 1: 3 by volume, so After be added in Rotary Evaporators progress rotary evaporation processing, obtain the precursor C that form is gel state；At the rotary evaporation The temperature of reason is 80 DEG C, and the time of the rotary evaporation processing is 50min；
Step 4: precursor C described in step 3 is carried out high-temperature heat treatment under the protection of reducibility gas, surpassed Grade capacitor graphene/LaMnO3Composite material；The reducibility gas is nitrogen hydrogen mixeding gas, the nitrogen hydrogen mixeding gas The volumn concentration of middle hydrogen is 5%, the detailed process of the high-temperature heat treatment are as follows: first with the heating rate of 100 DEG C/min 2h is kept the temperature after being warming up to 1000 DEG C, and 25 DEG C of room temperatures are then down to the rate of temperature fall of 5 DEG C/min.
To supercapacitor manufactured in the present embodiment graphene/LaMnO3Composite material carries out charge-discharge test, in electricity Under the conditions of current density is 0.5A/g, specific capacity value has reached 231F/g；Specific capacity is still after 1000 charge-discharge tests It is maintained at 95% or more.
Embodiment 3
The present embodiment supercapacitor graphene/LaMnO3The preparation method of composite material the following steps are included:
Step 1: graphene oxide ultrasonic disperse is obtained solution A in dehydrated alcohol；Graphite oxide in the solution A The concentration of alkene is 5mg/mL；
Step 2: by lanthanum acetylacetone and manganese acetylacetonate in molar ratio 1: 1 be uniformly mixed and be dissolved in propionic acid, obtain Solution B；The total concentration of metal cation is 0.8mol/L in the solution B；
Step 3: solution B described in solution A described in step 1 and step 2 is uniformly mixed at 1: 3 by volume, so After be added in Rotary Evaporators progress rotary evaporation processing, obtain the precursor C that form is gel state；At the rotary evaporation The temperature of reason is 100 DEG C, and the time of the rotary evaporation processing is 30min；
Step 4: precursor C described in step 3 is carried out high-temperature heat treatment under the protection of reducibility gas, surpassed Grade capacitor graphene/LaMnO3Composite material；The reducibility gas is argon hydrogen mixture, the argon hydrogen mixture The volumn concentration of middle hydrogen is 5%, the detailed process of the high-temperature heat treatment are as follows: first with the heating rate liter of 5 DEG C/min Then temperature is down to 25 DEG C of room temperatures to 3h is kept the temperature after 900 DEG C with the rate of temperature fall of 10 DEG C/min.
To supercapacitor manufactured in the present embodiment graphene/LaMnO3Composite material carries out charge-discharge test, in electricity Under the conditions of current density is 0.5A/g, specific capacity value has reached 240F/g；Specific capacity is still after 1000 charge-discharge tests It is maintained at 96% or more.
Embodiment 4
The present embodiment supercapacitor graphene/LaMnO3The preparation method of composite material the following steps are included:
Step 1: graphene oxide ultrasonic disperse is obtained solution A in dehydrated alcohol；Graphite oxide in the solution A The concentration of alkene is 2mg/mL；
Step 2: by lanthanum acetylacetone and manganese acetylacetonate in molar ratio 1: 1 be uniformly mixed and be dissolved in propionic acid, obtain Solution B；The total concentration of metal cation is 0.6mol/L in the solution B；
Step 3: solution B described in solution A described in step 1 and step 2 is uniformly mixed at 1: 1.5 by volume, It is then added to progress rotary evaporation processing in Rotary Evaporators, obtains the precursor C that form is gel state；The rotary evaporation The temperature of processing is 80 DEG C, and the time of the rotary evaporation processing is 40min；
Step 4: precursor C described in step 3 is carried out high-temperature heat treatment under the protection of reducibility gas, surpassed Grade capacitor graphene/LaMnO3Composite material；The reducibility gas is nitrogen hydrogen mixeding gas, the nitrogen hydrogen mixeding gas The volumn concentration of middle hydrogen is 4%, the detailed process of the high-temperature heat treatment are as follows: first with the heating rate liter of 80 DEG C/min Then temperature is down to 25 DEG C of room temperatures to 1.5h is kept the temperature after 1000 DEG C with the rate of temperature fall of 5 DEG C/min.
To supercapacitor manufactured in the present embodiment graphene/LaMnO3Composite material carries out charge-discharge test, in electricity Under the conditions of current density is 0.5A/g, specific capacity value has reached 224F/g；Specific capacity is still after 1000 charge-discharge tests It is maintained at 96% or more.
Embodiment 5
The present embodiment supercapacitor graphene/LaMnO3The preparation method of composite material the following steps are included:
Step 1: graphene oxide ultrasonic disperse is obtained solution A in dehydrated alcohol；Graphite oxide in the solution A The concentration of alkene is 4mg/mL；
Step 2: by lanthanum acetylacetone and manganese acetylacetonate in molar ratio 1: 1 be uniformly mixed and be dissolved in propionic acid, obtain Solution B；The total concentration of metal cation is 0.4mol/L in the solution B；
Step 3: solution B described in solution A described in step 1 and step 2 is uniformly mixed at 1: 2 by volume, so After be added in Rotary Evaporators progress rotary evaporation processing, obtain the precursor C that form is gel state；At the rotary evaporation The temperature of reason is 70 DEG C, and the time of the rotary evaporation processing is 60min；
Step 4: precursor C described in step 3 is carried out high-temperature heat treatment under the protection of reducibility gas, surpassed Grade capacitor graphene/LaMnO3Composite material；The reducibility gas is argon hydrogen mixture, the argon hydrogen mixture The volumn concentration of middle hydrogen is 5%, the detailed process of the high-temperature heat treatment are as follows: first with the heating rate of 150 DEG C/min 2h is kept the temperature after being warming up to 1100 DEG C, and 25 DEG C of room temperatures are then down to the rate of temperature fall of 5 DEG C/min.
To supercapacitor manufactured in the present embodiment graphene/LaMnO3Composite material carries out charge-discharge test, in electricity Under the conditions of current density is 0.5A/g, specific capacity value has reached 237F/g；Specific capacity is still after 1000 charge-discharge tests It is maintained at 96% or more.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention Protection scope in.

Claims (3)

1. a kind of supercapacitor graphene/LaMnO3The preparation method of composite material, which is characterized in that this method include with Lower step:
Step 1: graphene oxide ultrasonic disperse is obtained solution A in dehydrated alcohol；
Step 2: lanthanum acetylacetone and manganese acetylacetonate are after mixing dissolved in propionic acid at 1: 1 in molar ratio, solution is obtained B；
Step 3: by solution B described in solution A described in step 1 and step 2 by volume 1: (1 ~ 3) is uniformly mixed, then It is added to progress rotary evaporation processing in Rotary Evaporators, obtains the precursor C that form is gel state；
Step 4: precursor C described in step 3 is carried out high-temperature heat treatment under the protection of reducibility gas, capacitor is obtained With graphene/LaMnO3Composite material；The detailed process of the high-temperature heat treatment are as follows: first with 5 DEG C/min ~ 200 DEG C/min liter Warm rate keeps the temperature 1h ~ 3h after being warming up to 900 DEG C ~ 1100 DEG C, is then down to 25 DEG C with 2 DEG C/min ~ 10 DEG C/min rate of temperature fall Room temperature；
The concentration of graphene oxide is 2mg/mL ~ 5mg/mL in solution A described in step 1；
Reducibility gas described in step 4 is argon hydrogen mixture or nitrogen hydrogen mixeding gas, the argon hydrogen mixture and nitrogen hydrogen The volumn concentration of hydrogen is 4% ~ 5% in mixed gas.
2. supercapacitor according to claim 1 graphene/LaMnO3The preparation method of composite material, feature exist In the total concentration of metal cation is 0.1mol/L ~ 0.8mol/L in solution B described in step 2.
3. supercapacitor according to claim 1 graphene/LaMnO3The preparation method of composite material, feature exist In the temperature of, rotary evaporation described in step 3 processing be 70 DEG C ~ 100 DEG C, the time of the rotary evaporation processing be 30min ~ 60min。
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