CN102568843A - 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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- CN102568843A CN102568843A CN201010577480XA CN201010577480A CN102568843A CN 102568843 A CN102568843 A CN 102568843A CN 201010577480X A CN201010577480X A CN 201010577480XA CN 201010577480 A CN201010577480 A CN 201010577480A CN 102568843 A CN102568843 A CN 102568843A
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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-based manganese dioxide composite material.
[background technology]
Ultracapacitor is called the vast capacity electrochemical capacitor again, is a kind of novel energy-storing device between ordinary capacitor and secondary cell.The energy density of ultracapacitor storage is more than 10 times of traditional capacitor; Compare with battery; Have higher power density, the time that discharges and recharges is short, efficiency for charge-discharge is high, recycle advantages such as the life-span is long; Ultracapacitor also has operating temperature range wide (40 ℃～75 ℃) simultaneously; Therefore good reliability, characteristics 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 big, volume is little, energy density and power density are high.According to density energy formula E=1/2CU
2Can know, improve energy density, can reach through the mode that improves than electric capacity, wherein main relevant with its electrode material than electric capacity.Traditional electrode material mainly is a metal oxide, like manganese dioxide.Manganese dioxide electrode has high specific capacitance, advantage that cyclicity is good.But manganese dioxide is made the excessive problem of capacitor ubiquity resistance of electrode, needs in some way auxiliary material such as carbon to be joined to improve conductivity of electrolyte materials in the electrode material, improves the performance of capacitor.Expanded graphite is a kind of loose porous material that is made by native graphite, has numerous good characteristics such as low-density, higher specific surface area and excellent conducting performance.Therefore, can utilize high specific capacitance and the good cyclicity and the excellent conductive performance of expanded graphite of manganese dioxide, expanded graphite is combined to form novel composite material with manganese dioxide.The preparation method of traditional expanded graphite-based composite material is through preparing expanded graphite earlier, is that raw material reaction makes composite material again with the expanded graphite, needs a large amount of strong acid and strong oxidizer material, and technological operation is complicated, the raw material consumption is big, 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-based manganese dioxide composite material.
A kind of preparation method of expanded graphite-based manganese dioxide composite material comprises the steps: to provide divalent manganesetion compound, ammonium nitrate and graphite raw material, is configured to contain the suspension-turbid liquid of divalent manganesetion, ammonium nitrate and graphite; Acid-base value to the pH value of regulating suspension-turbid liquid is 0～2, and suspension-turbid liquid is heated to 150～200 degrees centigrade of following reactions 4～12 hours; Suspension-turbid liquid after the cooling reaction filters the collecting precipitation thing; Washing and dry sediment; Dried sediment is carried out calcination processing, obtain expanded graphite-based manganese dioxide composite material.
In preferred embodiment, the divalent manganesetion compound is a manganous salt.Further preferred, manganous salt is at least a in manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate and the manganese chloride.
In preferred embodiment, graphite raw material is a natural flake graphite.
In preferred embodiment, the concentration of ammonium nitrate is 4～12mol/L in the suspension-turbid liquid.
In preferred embodiment, the mol ratio of divalent manganesetion and ammonium nitrate is 1: 60～100 in the suspension-turbid liquid.
In preferred embodiment, it was that suspension-turbid liquid is placed hydrothermal reaction kettle in 4～12 hours that suspension-turbid liquid is heated to 150～200 degrees centigrade of following reactions, under 150～200 degrees centigrade, carried out hydro-thermal reaction 4～12 hours.
In preferred embodiment, washing is that at first to use distilled water washing precipitate to pH value be 6～7, uses absolute ethanol washing then 1～3 time.
In preferred embodiment, dry temperature is 40～100 degrees centigrade, and the dry time is 0.5～6 hour.
In preferred embodiment, the temperature of calcining is 300～500 degrees centigrade, and the time of calcining is 1～5 hour.
Above-mentioned preparation method directly uses graphite raw material and bivalent manganese reaction to generate expanded graphite-based manganese dioxide composite material, and expanded graphite and one step of manganese dioxide are synthetic, have avoided numerous and diverse operating procedures such as preparation expanded graphite; The consumption of acid that is used to regulate pH in the course of reaction is less, also need not a large amount of strong oxidizers, and technology is simple; The raw material materials are few, and environmental pollution is little, cost is low, simultaneously; Because be that a step is synthetic, raw material availability and productive rate are all higher.
[description of drawings]
Fig. 1 is the preparation flow figure of the expanded graphite-based manganese dioxide composite material of an execution mode;
Fig. 2 is the electron-microscope scanning figure of the expanded graphite-based manganese dioxide composite material of embodiment 3 preparations.
[embodiment]
Mainly combine accompanying drawing and specific embodiment that the preparation method of expanded graphite-based manganese dioxide composite material is done further detailed explanation below.
As shown in Figure 1, the preparation method of the expanded graphite-based 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 contain the suspension-turbid liquid of divalent manganesetion, ammonium nitrate and graphite.
Be the mixed solution that 1: 60～100 mixed is configured to contain divalent manganesetion in molar ratio at first with divalent manganesetion compound and ammonium nitrate; The concentration of ammonium nitrate is 4～12mol/L in the mixed solution; Then graphite raw material is scattered in this mixed solution; Stir, form finely dispersed suspension-turbid liquid.
Wherein, the divalent manganesetion compound can be manganous salts such as manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate or manganese chloride, perhaps contains the complex compound material of divalent manganesetion etc.
The preferred natural flake graphite of graphite, it is easy to draw materials, and cost is low.
Preferably, the concentration of ammonium nitrate is 8～12mol/L in the mixed solution; Further preferred, the concentration of ammonium nitrate is 9mol/L in the mixed solution.
Preferably, divalent manganesetion compound and ammonium nitrate are 1: 70～90 in molar ratio.
Step S120: acid-base value to the pH value of regulating suspension-turbid liquid is 0～2, and suspension-turbid liquid is heated to 150～200 degrees centigrade of following reactions 4～12 hours.
In this execution mode; At first use acid-base value that inorganic acids such as nitric acid, phosphoric acid, hydrochloric acid or sulfuric acid regulate suspension-turbid liquids to pH be 0～2; Then highly acid suspension-turbid liquid is placed hydrothermal reaction kettle, react down at 150～200 degrees centigrade and carried out hydro-thermal reaction 4～12 hours.Preferably, the temperature of hydro-thermal reaction is 160～180 degrees centigrade, and the reaction time is 4～8 hours; Further preferred, the temperature of hydro-thermal reaction is 180 degrees centigrade, 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 the use of numerous and diverse catalytic oxidation system, and cost is low, and the reduzate easy-clear.
Step S130: product is cooled to room temperature, filters the collecting precipitation thing.
Step S140: the washing and dry sediment: at first use the distilled water washing precipitate to pH be 6～7, re-use absolute ethanol washing 1～3 time.Preferably, dry temperature is 40～100 degrees centigrade, and the dry time is 0.5～6 hour.
Step S150: dried sediment is carried out calcination processing, obtain expanded graphite-based manganese dioxide composite material.
Desciccate among the step S140 is transferred in the crucible, calcined 1～5 hour down, graphite raw material is fully expanded, generate expanded graphite-based manganese bioxide material in 300～500 degrees centigrade.Preferably, calcining heat is 350 degrees centigrade, and calcination time is 2 hours, calcines in inert gas or N
2Carry out in the atmosphere.
Above-mentioned preparation method directly uses graphite raw material and bivalent manganese reaction to generate expanded graphite-based manganese dioxide composite material, and expanded graphite and one step of manganese dioxide are synthetic, have avoided numerous and diverse operating procedures such as preparation expanded graphite; The consumption of acid that is used to regulate pH in the course of reaction is less, also need not a large amount of strong oxidizers, and technology is simple; The raw material materials are few, and environmental pollution is little, cost is low, simultaneously; Because be that a step is synthetic, raw material availability and productive rate are all higher.
Below be the specific embodiment part:
Embodiment 1
The expanded graphite-based MnO of present embodiment
2The preparation method of composite material comprises the steps:
(1) manganese nitrate and ammonium nitrate are mixed with mixed solution; The concentration of ammonium nitrate is 9mol/L in the mixed solution; The mol ratio of manganese nitrate and ammonium nitrate is 1: 80, and the 0.5005g natural flake graphite is scattered in the above-mentioned mixed solution, stirs to form finely dispersed suspension-turbid liquid;
(2) acid-base value to the pH value of adding nitric acid adjusting suspension-turbid liquid is 0～2, again this suspension-turbid liquid is changed in the hydrothermal reaction kettle, and under 180 ℃ of temperature, hydro-thermal reaction 8 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) using distilled water washing precipitate to pH value is 6～7, uses absolute ethanol washing at last 2 times; Again with sediment under 60 ℃ of baking temperatures in vacuum drying chamber dry 2 hours;
(5) dried deposition is transferred in the crucible, insulation is 2 hours under 350 ℃ of calcining heats, obtains expanded graphite-based MnO
2Composite material.
Embodiment 2
The expanded graphite-based MnO of present embodiment
2The preparation method of composite material comprises the steps:
(1) manganese sulfate and ammonium nitrate are mixed with mixed solution; The concentration of ammonium nitrate is 4mol/L in the mixed solution; The mol ratio of manganese sulfate and ammonium nitrate is 1: 60, and the 0.5000g natural flake graphite is scattered in the above-mentioned mixed solution, stirs to form finely dispersed suspension-turbid liquid;
(2) acid-base value to the pH value of adding hydrochloric acid adjusting suspension-turbid liquid is 0～2, again this suspension-turbid liquid is changed in the hydrothermal reaction kettle, and under 150 ℃ of temperature, hydro-thermal reaction 4 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) using distilled water washing precipitate to pH value is 6～7, uses absolute ethanol washing at last 2 times; Again with sediment under 50 ℃ of baking temperatures in vacuum drying chamber dry 1 hour;
(5) dried deposition is transferred in the crucible, insulation is 1 hour under 300 ℃ of calcining heats, obtains expanded graphite-based MnO
2Composite material.
Embodiment 3
The expanded graphite-based MnO of present embodiment
2The preparation method of composite material comprises the steps:
(1) manganese chloride and ammonium nitrate are mixed with mixed solution; The concentration of ammonium nitrate is 6mol/L in the mixed solution; The mol ratio of manganese chloride and ammonium nitrate is 1: 70, and the 0.5012g natural flake graphite is scattered in the above-mentioned mixed solution, stirs to form finely dispersed suspension-turbid liquid;
(2) acid-base value to the pH value of adding phosphoric acid adjusting suspension-turbid liquid is 0～2, again this suspension-turbid liquid is changed in the hydrothermal reaction kettle, and under 160 ℃ of temperature, hydro-thermal reaction 6 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) using distilled water washing precipitate to pH value is 6～7, uses absolute ethanol washing at last 2 times; Again with sediment under 70 ℃ of baking temperatures in vacuum drying chamber dry 3 hours;
(5) dried deposition is transferred in the crucible, insulation is 2 hours under 400 ℃ of calcining heats, obtains expanded graphite-based MnO
2Composite material.
Be illustrated in figure 2 as the electron-microscope scanning figure of the expanded graphite-based MnO2 composite material that present embodiment makes, from electron-microscope scanning figure, can find out: edge and inwall at expanded graphite have a large amount of nano-scale particles with nanometer diameter, and this is MnO
2Nano particle; MnO
2The nano particle majority is distributed in the edge of expanded graphite layer, is distributed on a small quantity in the expanded graphite hole.
Embodiment 4
The expanded graphite-based MnO of present embodiment
2The preparation method of composite material comprises the steps:
(1) manganese carbonate and ammonium nitrate are mixed with mixed solution; The concentration of ammonium nitrate is 8mol/L in the mixed solution; The mol ratio of manganese carbonate and ammonium nitrate is 1: 80, and the 0.5033g natural flake graphite is scattered in the above-mentioned mixed solution, stirs to form finely dispersed suspension-turbid liquid;
(2) acid-base value to the pH value of the mixed acid of adding nitric acid and hydrochloric acid adjusting suspension-turbid liquid is 0～2, again this suspension-turbid liquid is changed in the hydrothermal reaction kettle, and under 170 ℃ of temperature, hydro-thermal reaction 8 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) using distilled water washing precipitate to pH value is 6～7, uses absolute ethanol washing at last 2 times; Again with sediment under 80 ℃ of baking temperatures in vacuum drying chamber dry 4 hours;
(5) dried deposition is transferred in the crucible, insulation is 3 hours under 450 ℃ of calcining heats, obtains expanded graphite-based MnO
2Composite material.
Embodiment 5
The expanded graphite-based MnO of present embodiment
2The preparation method of composite material comprises the steps:
(1) manganese nitrate and ammonium nitrate are mixed with mixed solution; The concentration of ammonium nitrate is 10mol/L in the mixed solution; The mol ratio of manganese nitrate and ammonium nitrate is 1: 90, and the 0.5015g natural flake graphite is scattered in the above-mentioned mixed solution, stirs to form finely dispersed suspension-turbid liquid;
(2) acid-base value to the pH value of the mixed acid of adding nitric acid and phosphoric acid adjusting suspension-turbid liquid is 0～2, again this suspension-turbid liquid is changed in the hydrothermal reaction kettle, and under 190 ℃ of temperature, hydro-thermal reaction 10 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) using distilled water washing precipitate to pH value is 6～7, uses absolute ethanol washing at last 2 times; Again with sediment under 90 ℃ of baking temperatures in vacuum drying chamber dry 5 hours;
(5) dried deposition is transferred in the crucible, insulation is 4 hours under 500 ℃ of calcining heats, obtains expanded graphite-based MnO
2Composite material.
Embodiment 6
The expanded graphite-based MnO of present embodiment
2The preparation method of composite material comprises the steps:
(1) manganese nitrate and ammonium nitrate are mixed with mixed solution; The concentration of ammonium nitrate is 12mol/L in the mixed solution; The mol ratio of manganese nitrate and ammonium nitrate is 1: 100, and the 0.5025g natural flake graphite is scattered in the above-mentioned mixed solution, stirs to form finely dispersed suspension-turbid liquid;
(2) acid-base value to the pH value of adding nitric acid adjusting suspension-turbid liquid is 0～2, again this suspension-turbid liquid is changed in the hydrothermal reaction kettle, and under 200 ℃ of temperature, hydro-thermal reaction 12 hours;
(3) reacted suspension-turbid liquid is naturally cooled to room temperature, filter to isolate sediment;
(4) using distilled water washing precipitate to pH value is 6～7, uses absolute ethanol washing at last 2 times; Again with sediment under 100 ℃ of baking temperatures in vacuum drying chamber dry 6 hours;
(5) dried deposition is transferred in the crucible, insulation is 5 hours under 350 ℃ of calcining heats, obtains expanded graphite-based MnO
2Composite material.
The expanded graphite-based MnO that the foregoing description obtains
2Composite material can be widely used in the manufacturing field in ultracapacitor field.
Below be expanded graphite-based MnO
2The test of the capacitive property of composite material: with absolute ethyl alcohol as dispersant, with expanded graphite-based MnO
2Composite material and binding agent (polytetrafluoroethylene) are that 90: 10 mixed is coated on the nickel foam collector dry back compression moulding after evenly by mass ratio.Ultracapacitor adopts three-electrode system, and (reference electrode is a 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
Can find out from table 1, adopt expanded graphite-based MnO
2The ultracapacitor of the making of composite material is more higher than electric capacity, better performances.
The above embodiment has only expressed several kinds of execution modes of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art under the prerequisite that does not break away from the present invention's design, 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 accompanying claims.
Claims (10)
1. the preparation method of an expanded graphite-based 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 contain the suspension-turbid liquid of divalent manganesetion, ammonium nitrate and graphite;
Acid-base value to the pH value of regulating said suspension-turbid liquid is 0～2, and said suspension-turbid liquid is heated to 150～200 degrees centigrade of following reactions 4～12 hours;
Suspension-turbid liquid after the cooling reaction filters the collecting precipitation thing;
Washing and dry said sediment;
Dried said sediment is carried out calcination processing, obtain said expanded graphite-based manganese dioxide composite material.
2. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1 is characterized in that, said divalent manganesetion compound is a manganous salt.
3. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 2 is characterized in that, said manganous salt is at least a in manganese sulfate, manganese carbonate, manganese phosphate, manganese nitrate and the manganese chloride.
4. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1 is characterized in that, said graphite raw material is a natural flake graphite.
5. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1 is characterized in that, the concentration of ammonium nitrate is 4～12mol/L in the said suspension-turbid liquid.
6. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1 is characterized in that, the mol ratio of divalent manganesetion and ammonium nitrate is 1: 60～100 in the said suspension-turbid liquid.
7. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1; It is characterized in that; Said with said suspension-turbid liquid be heated to 150～200 degrees centigrade down reaction be that said suspension-turbid liquid is placed hydrothermal reaction kettle in 4～12 hours, under 150～200 degrees centigrade, carried out hydro-thermal reaction 4～12 hours.
8. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1 is characterized in that, said washing is that at first to use distilled water washing precipitate to pH value be 6～7, uses absolute ethanol washing then 1～3 time.
9. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1 is characterized in that, the temperature of said drying is 40～100 degrees centigrade, and the dry time is 0.5～6 hour.
10. the preparation method of expanded graphite-based manganese dioxide composite material as claimed in claim 1 is characterized in that, the temperature of said calcining is 300～500 degrees centigrade, and the time of calcining is 1～5 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104916832A (en) * | 2015-07-09 | 2015-09-16 | 山西大学 | Method for preparing high performance flexible negative electrode materials |
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| CN1224693A (en) * | 1998-01-24 | 1999-08-04 | 北京华锐新材料技术发展有限公司 | Chemical graft process to prepare expansive graphite |
| 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 |
| US20040048162A1 (en) * | 2000-03-06 | 2004-03-11 | Barsukov Igor V. | Engineered carbonaceous materials and power sources using these materials |
| CN101060038A (en) * | 2007-04-20 | 2007-10-24 | 哈尔滨工程大学 | Expanded graphite/metal oxide composite material and preparation method thereof |
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2010
- 2010-12-07 CN CN201010577480.XA patent/CN102568843B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224693A (en) * | 1998-01-24 | 1999-08-04 | 北京华锐新材料技术发展有限公司 | Chemical graft process to prepare expansive graphite |
| US20040048162A1 (en) * | 2000-03-06 | 2004-03-11 | Barsukov Igor V. | 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 |
| CN101060038A (en) * | 2007-04-20 | 2007-10-24 | 哈尔滨工程大学 | Expanded graphite/metal oxide composite material and preparation method thereof |
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| 《Applied Energy》 20080710 T.X. Li等 Performance study of a consolidated manganese chloride-expanded graphite compound for sorption deep-freezing processes , * |
| T.X. LI等: "Performance study of a consolidated manganese chloride–expanded graphite compound for sorption deep-freezing processes", 《APPLIED ENERGY》, 10 July 2008 (2008-07-10) * |
| 万传云等: "不同工作介质下二氧化锰/膨胀石墨复合材料的电化学电容器行为", 《化学学报》, vol. 65, no. 17, 31 December 2007 (2007-12-31), pages 1911 - 1916 * |
Cited By (1)
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|---|---|---|---|---|
| CN104916832A (en) * | 2015-07-09 | 2015-09-16 | 山西大学 | Method for preparing high performance flexible negative electrode materials |
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