CN102568843B - Preparation method of expanded graphite base manganese dioxide composite material - Google Patents
Preparation method of expanded graphite base manganese dioxide composite material Download PDFInfo
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- CN102568843B CN102568843B CN201010577480.XA CN201010577480A CN102568843B CN 102568843 B CN102568843 B CN 102568843B CN 201010577480 A CN201010577480 A CN 201010577480A CN 102568843 B CN102568843 B CN 102568843B
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Abstract
The invention relates to a preparation method of an expanded graphite base manganese dioxide composite material, wherein the expanded graphite base manganese dioxide composite material is obtained by reaction of a graphite material and bivalent manganese; As the expanded graphite and the manganese dioxide are synthesized by one step, the complex operation step for preparing expanded graphite is avoided, dosage of the acid for regulating pH during the reaction is less, a great amount of strong oxidants are not needed, the process is simple, the dosage of the raw material is less, the environment pollution is less and the cost is low; due to one-step synthesis, the utilization rate of the material and the yield rate are high.
Description
[technical field]
The present invention relates to the preparation field of electrochemical material, relate in particular to a kind of preparation method of expanded graphite base manganese dioxide composite material.
[background technology]
Ultracapacitor is called again vast capacity electrochemical capacitor, is a kind of Novel energy storage apparatus between ordinary capacitor and secondary cell.It is more than 10 times that the energy density of ultracapacitor storage is traditional capacitor, compare with battery, the advantage such as there is higher power density, the time that discharges and recharges is short, efficiency for charge-discharge is high, service life cycle is long, ultracapacitor also has operating temperature range wide (40 ℃～75 ℃) simultaneously, good reliability, therefore the features such as the energy-conservation energy and environmental protection, can be widely used as the igniter etc. of stand-by power supply, solar charger, warning device, household electrical appliance, camera flashlamp and the aircraft of microcomputer.
The basic demand of ultracapacitor is that capacity is large, volume is little, energy density and power density high.According to density energy formula E=1/2CU
2known, improve energy density, can reach by putting forward the mode of high specific capacitance, wherein main relevant with its electrode material than electric capacity.Traditional electrode material is mainly metal oxide, as manganese dioxide.Manganese dioxide electrode has advantages of that high specific capacitance, cyclicity are good.But manganese dioxide is made the excessive problem of capacitor ubiquity resistance of electrode, need in some way the auxiliary material such as carbon be joined to the conductivity that improves material in electrode material, improve the performance of capacitor.Expanded graphite is a kind of loose porous material being made by native graphite, has low-density, higher specific area and good numerous good characteristics such as electric conductivity.Therefore, can utilize high specific capacitance and good cyclicity and the excellent conductive performance of expanded graphite of manganese dioxide, expanded graphite is combined with manganese dioxide and form novel composite material.The preparation method of traditional expanded graphite-based composite material is by first preparing expanded graphite, then take expanded graphite and make composite material as raw material reaction, needs a large amount of strong acid and strong oxidizer material, and complex operation, raw material consumption are large, and cost is high.
[summary of the invention]
Based on this, be necessary to provide a kind of preparation method of simple to operate, lower-cost expanded graphite base manganese dioxide composite material.
A preparation method for expanded graphite base manganese dioxide composite material, comprises the steps: to provide divalent manganesetion compound, ammonium nitrate and graphite raw material, is configured to the suspension-turbid liquid containing divalent manganesetion, ammonium nitrate and graphite; Regulating acid-base value to the pH value of suspension-turbid liquid is 0～2, and suspension-turbid liquid is heated to react 4～12 hours under 150～200 degrees Celsius; Cooling reacted suspension-turbid liquid, filters collecting precipitation thing; Washing dry sediment; Dried sediment is carried out to calcination processing, obtain expanded graphite base manganese dioxide composite material.
In a preferred embodiment, divalent manganesetion compound is manganous salt.Further preferred, manganous salt is at least one in manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate and manganese chloride.
In a preferred embodiment, graphite raw material is natural flake graphite.
In a preferred embodiment, in suspension-turbid liquid, the concentration of ammonium nitrate is 4～12mol/L.
In a preferred embodiment, in suspension-turbid liquid, the mol ratio of divalent manganesetion and ammonium nitrate is 1: 60～100.
In a preferred embodiment, it is that suspension-turbid liquid is placed in to hydrothermal reaction kettle that suspension-turbid liquid is heated to react 4～12 hours under 150～200 degrees Celsius, carries out hydro-thermal reaction 4～12 hours under 150～200 degrees Celsius.
In a preferred embodiment, washing is that first to use distilled water washing precipitate to pH value be 6～7, then uses absolute ethanol washing 1～3 time.
In a preferred embodiment, dry temperature is 40～100 degrees Celsius, and the dry time is 0.5～6 hour.
In a preferred embodiment, the temperature of calcining is 300～500 degrees Celsius, and the time of calcining is 1～5 hour.
Above-mentioned preparation method directly uses graphite raw material to react with bivalent manganese and generates expanded graphite base manganese dioxide composite material, expanded graphite and manganese dioxide one-step synthesis, avoided preparing numerous and diverse operating procedures such as expanded graphite, in course of reaction for regulating the sour consumption of pH less, also without a large amount of strong oxidizers, technique is simple, raw material materials are few, and environmental pollution is little, cost is low, simultaneously, owing to being one-step synthesis, raw material availability and productive rate are all higher.
[accompanying drawing explanation]
Fig. 1 is the preparation flow figure of the expanded graphite base manganese dioxide composite material of an execution mode;
Fig. 2 is the electron-microscope scanning figure of the expanded graphite base manganese dioxide composite material of embodiment 3 preparations.
[embodiment]
Below mainly in conjunction with the drawings and the specific embodiments the preparation method of expanded graphite base manganese dioxide composite material is described in further detail.
As shown in Figure 1, the preparation method of the expanded graphite base manganese dioxide composite material of an execution mode, comprises the steps:
Step S110: divalent manganesetion compound, ammonium nitrate and graphite raw material are provided, are configured to the suspension-turbid liquid containing divalent manganesetion, ammonium nitrate and graphite.
First by divalent manganesetion compound and ammonium nitrate, be that 1: 60～100 ratio is mixedly configured into the mixed solution containing divalent manganesetion in molar ratio, in mixed solution, the concentration of ammonium nitrate is 4～12mol/L, then graphite raw material is scattered in this mixed solution, stir, form finely dispersed suspension-turbid liquid.
Wherein, divalent manganesetion compound can be the manganous salts such as manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate or manganese chloride, or containing the complex compound material of divalent manganesetion etc.
The preferred natural flake graphite of graphite, draws materials easy, and cost is low.
Preferably, in mixed solution, the concentration of ammonium nitrate is 8～12mol/L; Further preferred, in mixed solution, the concentration of ammonium nitrate is 9mol/L.
Preferably, divalent manganesetion compound and ammonium nitrate are 1: 70～90 in molar ratio.
Step S120: regulating acid-base value to the pH value of suspension-turbid liquid is 0～2, and suspension-turbid liquid is heated to react 4～12 hours under 150～200 degrees Celsius.
In present embodiment, first use acid-base value that the inorganic acid such as nitric acid, phosphoric acid, hydrochloric acid or sulfuric acid regulates suspension-turbid liquids to pH be 0～2, then highly acid suspension-turbid liquid is placed in to hydrothermal reaction kettle, under 150～200 degrees Celsius, reaction is carried out hydro-thermal reaction 4～12 hours.Preferably, the temperature of hydro-thermal reaction is 160～180 degrees Celsius, and the reaction time is 4～8 hours; Further preferred, the temperature of hydro-thermal reaction is 180 degrees Celsius, and the reaction time is 8 hours.
Ammonium nitrate can be used as oxidation catalyst under the environment of strong acid, the generation oxidation reaction of catalysis divalent manganesetion, and reaction efficiency is higher, can avoid using numerous and diverse catalytic oxidation system, and cost is low, and reduzate easy-clear.
Step S130: product is cooled to room temperature, filters collecting precipitation thing.
Step S140: washing and dry sediment: first use distilled water washing precipitate to pH be 6～7, re-use absolute ethanol washing 1～3 time.Preferably, dry temperature is 40～100 degrees Celsius, and the dry time is 0.5～6 hour.
Step S150: dried sediment is carried out to calcination processing, obtain expanded graphite base manganese dioxide composite material.
Desciccate in step S140 is transferred in crucible, under 300～500 degrees Celsius, calcines 1～5 hour, graphite raw material is fully expanded, generate expanded graphite-based manganese bioxide material.Preferably, calcining heat is 350 degrees Celsius, and calcination time is 2 hours, calcines in inert gas or N
2in atmosphere, carry out.
Above-mentioned preparation method directly uses graphite raw material to react with bivalent manganese and generates expanded graphite base manganese dioxide composite material, expanded graphite and manganese dioxide one-step synthesis, avoided preparing numerous and diverse operating procedures such as expanded graphite, in course of reaction for regulating the sour consumption of pH less, also without a large amount of strong oxidizers, technique is simple, raw material materials are few, and environmental pollution is little, cost is low, simultaneously, owing to being one-step synthesis, raw material availability and productive rate are all higher.
Be below specific embodiment part:
Embodiment 1
The expanded graphite-based MnO of the present embodiment
2the preparation method of composite material, comprises the steps:
(1) manganese nitrate and ammonium nitrate are mixed with to mixed solution, in mixed solution, the concentration of ammonium nitrate is 9mol/L, the mol ratio of manganese nitrate and ammonium nitrate is 1: 80, and 0.5005g natural flake graphite is scattered in above-mentioned mixed solution, stirs and forms finely dispersed suspension-turbid liquid;
(2) adding nitric acid to regulate acid-base value to the pH value of suspension-turbid liquid is 0～2, then this suspension-turbid liquid is proceeded in hydrothermal reaction kettle, at 180 ℃ of temperature, and hydro-thermal reaction 8 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) by distilled water washing precipitate to pH value, be 6～7, finally use absolute ethanol washing 2 times; Again sediment is dried to 2 hours under 60 ℃ of baking temperatures in vacuum drying chamber;
(5) dried precipitation is transferred in crucible, under 350 ℃ of calcining heats, is incubated 2 hours, obtain expanded graphite-based MnO
2composite material.
Embodiment 2
The expanded graphite-based MnO of the present embodiment
2the preparation method of composite material, comprises the steps:
(1) manganese sulfate and ammonium nitrate are mixed with to mixed solution, in mixed solution, the concentration of ammonium nitrate is 4mol/L, the mol ratio of manganese sulfate and ammonium nitrate is 1: 60, and 0.5000g natural flake graphite is scattered in above-mentioned mixed solution, stirs and forms finely dispersed suspension-turbid liquid;
(2) adding hydrochloric acid to regulate acid-base value to the pH value of suspension-turbid liquid is 0～2, then this suspension-turbid liquid is proceeded in hydrothermal reaction kettle, at 150 ℃ of temperature, and hydro-thermal reaction 4 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) by distilled water washing precipitate to pH value, be 6～7, finally use absolute ethanol washing 2 times; Again sediment is dried to 1 hour under 50 ℃ of baking temperatures in vacuum drying chamber;
(5) dried precipitation is transferred in crucible, under 300 ℃ of calcining heats, is incubated 1 hour, obtain expanded graphite-based MnO
2composite material.
Embodiment 3
The expanded graphite-based MnO of the present embodiment
2the preparation method of composite material, comprises the steps:
(1) manganese chloride and ammonium nitrate are mixed with to mixed solution, in mixed solution, the concentration of ammonium nitrate is 6mol/L, the mol ratio of manganese chloride and ammonium nitrate is 1: 70, and 0.5012g natural flake graphite is scattered in above-mentioned mixed solution, stirs and forms finely dispersed suspension-turbid liquid;
(2) adding phosphoric acid to regulate acid-base value to the pH value of suspension-turbid liquid is 0～2, then this suspension-turbid liquid is proceeded in hydrothermal reaction kettle, at 160 ℃ of temperature, and hydro-thermal reaction 6 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) by distilled water washing precipitate to pH value, be 6～7, finally use absolute ethanol washing 2 times; Again sediment is dried to 3 hours under 70 ℃ of baking temperatures in vacuum drying chamber;
(5) dried precipitation is transferred in crucible, under 400 ℃ of calcining heats, is incubated 2 hours, obtain expanded graphite-based MnO
2composite material.
The electron-microscope scanning figure that is illustrated in figure 2 the expanded graphite-based MnO2 composite material that the present embodiment makes can find out: edge and inwall at expanded graphite have a large amount of nano-scale particles with nanometer diameter, and this is MnO from electron-microscope scanning figure
2nano particle; MnO
2nano particle majority is distributed in the edge of expanded graphite layer, is distributed on a small quantity in expanded graphite hole.
Embodiment 4
The expanded graphite-based MnO of the present embodiment
2the preparation method of composite material, comprises the steps:
(1) manganese carbonate and ammonium nitrate are mixed with to mixed solution, in mixed solution, the concentration of ammonium nitrate is 8mol/L, the mol ratio of manganese carbonate and ammonium nitrate is 1: 80, and 0.5033g natural flake graphite is scattered in above-mentioned mixed solution, stirs and forms finely dispersed suspension-turbid liquid;
(2) adding acid-base value to the pH value of the mixed acid adjusting suspension-turbid liquid of nitric acid and hydrochloric acid is 0～2, then this suspension-turbid liquid is proceeded in hydrothermal reaction kettle, at 170 ℃ of temperature, and hydro-thermal reaction 8 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) by distilled water washing precipitate to pH value, be 6～7, finally use absolute ethanol washing 2 times; Again sediment is dried to 4 hours under 80 ℃ of baking temperatures in vacuum drying chamber;
(5) dried precipitation is transferred in crucible, under 450 ℃ of calcining heats, is incubated 3 hours, obtain expanded graphite-based MnO
2composite material.
Embodiment 5
The expanded graphite-based MnO of the present embodiment
2the preparation method of composite material, comprises the steps:
(1) manganese nitrate and ammonium nitrate are mixed with to mixed solution, in mixed solution, the concentration of ammonium nitrate is 10mol/L, the mol ratio of manganese nitrate and ammonium nitrate is 1: 90, and 0.5015g natural flake graphite is scattered in above-mentioned mixed solution, stirs and forms finely dispersed suspension-turbid liquid;
(2) adding acid-base value to the pH value of the mixed acid adjusting suspension-turbid liquid of nitric acid and phosphoric acid is 0～2, then this suspension-turbid liquid is proceeded in hydrothermal reaction kettle, at 190 ℃ of temperature, and hydro-thermal reaction 10 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) by distilled water washing precipitate to pH value, be 6～7, finally use absolute ethanol washing 2 times; Again sediment is dried to 5 hours under 90 ℃ of baking temperatures in vacuum drying chamber;
(5) dried precipitation is transferred in crucible, under 500 ℃ of calcining heats, is incubated 4 hours, obtain expanded graphite-based MnO
2composite material.
Embodiment 6
The expanded graphite-based MnO of the present embodiment
2the preparation method of composite material, comprises the steps:
(1) manganese nitrate and ammonium nitrate are mixed with to mixed solution, in mixed solution, the concentration of ammonium nitrate is 12mol/L, the mol ratio of manganese nitrate and ammonium nitrate is 1: 100, and 0.5025g natural flake graphite is scattered in above-mentioned mixed solution, stirs and forms finely dispersed suspension-turbid liquid;
(2) adding nitric acid to regulate acid-base value to the pH value of suspension-turbid liquid is 0～2, then this suspension-turbid liquid is proceeded in hydrothermal reaction kettle, at 200 ℃ of temperature, and hydro-thermal reaction 12 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) by distilled water washing precipitate to pH value, be 6～7, finally use absolute ethanol washing 2 times; Again sediment is dried to 6 hours under 100 ℃ of baking temperatures in vacuum drying chamber;
(5) dried precipitation is transferred in crucible, under 350 ℃ of calcining heats, is incubated 5 hours, obtain expanded graphite-based MnO
2composite material.
The expanded graphite-based MnO that above-described embodiment obtains
2composite material can be widely used in the manufacture field in ultracapacitor field.
Be below expanded graphite-based MnO
2the capacitive property test of composite material: using absolute ethyl alcohol as dispersant, by expanded graphite-based MnO
2after mixing, the ratio that composite material is 90: 10 with binding agent (polytetrafluoroethylene) is in mass ratio coated on nickel foam collector, and dry rear compressing.Ultracapacitor adopts three-electrode system, and (reference electrode is saturated calomel electrode, and auxiliary electrode is large-area nickel foam sheet, and work electrode is the expanded graphite-based MnO of each embodiment gained
2composite electrode), utilize the expanded graphite-based MnO of CH1660A electrochemical workstation to each embodiment gained
2the electrochemical capacitor performance of composite material is tested.It is more as shown in table 1 below than electric capacity.
The expanded graphite-based MnO of each embodiment gained of table 1
2the ratio capacitance data of composite material
As can be seen from Table 1, adopt expanded graphite-based MnO
2the ultracapacitor of the making of composite material is higher than electric capacity, better performances.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a preparation method for expanded graphite base manganese dioxide composite material, is characterized in that, comprises the steps:
Divalent manganesetion compound, ammonium nitrate and graphite raw material are provided, are configured to the suspension-turbid liquid containing divalent manganesetion, ammonium nitrate and graphite raw material, wherein, in described suspension-turbid liquid, the mol ratio of divalent manganesetion and ammonium nitrate is 1:60～100;
Regulating acid-base value to the pH value of described suspension-turbid liquid is 0～2, and described suspension-turbid liquid is heated to react 4～12 hours at 150～200 ℃;
Cooling reacted suspension-turbid liquid, filters collecting precipitation thing;
Wash and be dried described sediment;
Dried described sediment is carried out to calcination processing, obtain described expanded graphite base manganese dioxide composite material, the temperature of described calcining is 300～500 ℃.
2. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 1, is characterized in that, described divalent manganesetion compound is manganous salt.
3. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 2, is characterized in that, described manganous salt is at least one in manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate and manganese chloride.
4. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 1, is characterized in that, described graphite raw material is natural flake graphite.
5. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 1, is characterized in that, in described suspension-turbid liquid, the concentration of ammonium nitrate is 4～12mol/L.
6. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 1, it is characterized in that, described described suspension-turbid liquid is heated to react at 150～200 ℃ 4～12 hours is that described suspension-turbid liquid is placed in to hydrothermal reaction kettle, at 150～200 ℃, carries out hydro-thermal reaction 4～12 hours.
7. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 1, is characterized in that, described washing is that first to use distilled water washing precipitate to pH value be 6～7, then uses absolute ethanol washing 1～3 time.
8. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 1, is characterized in that, described dry temperature is 40～100 ℃, and the dry time is 0.5～6 hour.
9. the preparation method of expanded graphite base manganese dioxide composite material as claimed in claim 1, is characterized in that, the time of calcining is 1～5 hour.
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| US6660434B2 (en) * | 2000-03-06 | 2003-12-09 | Superior Graphite Co. | Engineered carbonaceous materials and power sources using these materials |
| US6451486B1 (en) * | 2000-05-01 | 2002-09-17 | The Gillette Company | Battery cathode including a mixture of manganese dioxide with carbon particles of expanded and non-expanded graphite |
| CN100541688C (en) * | 2007-04-20 | 2009-09-16 | 哈尔滨工程大学 | Preparation method of expanded graphite/metal oxide composite material |
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