CN102306551A - Porous moulded carbon/manganese oxide nano compound material and preparation method thereof - Google Patents
Porous moulded carbon/manganese oxide nano compound material and preparation method thereof Download PDFInfo
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- CN102306551A CN102306551A CN201110133138A CN201110133138A CN102306551A CN 102306551 A CN102306551 A CN 102306551A CN 201110133138 A CN201110133138 A CN 201110133138A CN 201110133138 A CN201110133138 A CN 201110133138A CN 102306551 A CN102306551 A CN 102306551A
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Abstract
The invention discloses a porous moulded carbon/manganese oxide nano compound material and a preparation method thereof and belongs to the field of electrochemistry and new energy materials. The compound material comprises 2 to 98 percent of porous moulded carbon and 98 to 2 percent of manganese oxide; the pore diameter of the porous moulded carbon is 5 nanometres to 10 microns; the grain diameter of the porous moulded carbon/manganese oxide nano compound material is 5 nanometres to 10 millimetres; the density of the porous moulded carbon/manganese oxide nano compound material is 1-4g/cm<3>; and the total specific surface area of the porous moulded carbon/manganese oxide nano compound material is 50-1,500g/cm<2>. The porous moulded carbon/manganese oxide nano compound material which is prepared from cheap manganese-containing materials and porous moulded carbon through ultrasonic reduction and thermal treatment has relatively high conductivity and a large specific surface area; when the porous moulded carbon/manganese oxide nano compound material is used as an electrode material of a supercapacitor, the specific capacity in an aqueous electrolyte can reach 300F/g and the specific capacity in an organic system can reach 200F/g; and the preparation method for the porous moulded carbon/manganese oxide nano compound material is simple and is applicable to industrial production and the porous moulded carbon/manganese oxide nano compound material can be used as an ideal electrode material for the supercapacitor.
Description
Technical field
The invention discloses the method for a kind of multi-hole casting carbon/manganese oxide nano composite material, belong to electrochemistry and new energy materials field.
Background technology
Energy shortage and environmental pollution are the significant challenge that current mankind faces, and development is green, reproducible energy storage device is the important topic of pendulum in face of the mankind.Ultracapacitor is as a kind of new green power memory device; Have than much bigger energy density of traditional capacitor and the power density more much higher, have extremely wide application prospect in fields such as traffic, mobile communication, information technology, Aero-Space and science and techniques of defence than battery.
The electrode material that is used for ultracapacitor at present mainly contains carbon, transition metal oxide and conducting polymer.Material with carbon element is current research and uses electrode material for super capacitor the most widely that it mainly comprises activated carbon, activated carbon fiber, carbon nano-tube and Graphene etc.Wherein, active carbon material is widely adopted in present ultracapacitor commodity owing to have stable useful life, cheap price and large-scale industrial production basis.But the active carbon material ratio is easier to oxidized, causes the internal resistance of carbon back ultracapacitor bigger, and high frequency characteristics is poor, and the conductivity of active carbon material is relatively poor.Many defectives allow it be difficult to satisfy the active demand to ultracapacitor high-energy, high power density such as electric automobile.Conducting polymer has the shortcoming of cyclical stability difference.This just needs the scientific research personnel to find more suitably new material.
Manganese is the element that contains flow control 12 in the earth's crust; Abundance is high; Manganese dioxide class material; Has remarkable advantage cheap, environmentally friendly and that the electrochemistry operation window is wide; The more important thing is; The manganese dioxide based super capacitor can adopt neutral electrolyte solution (like aqueous solution of sodium sulphate, potassium chloride etc.), and must adopt the strong acid and strong base electrolyte unlike other metal oxides or carbon back ultracapacitor, and this makes the assembling of manganese dioxide based super capacitor and uses safer, more convenient.Manganese oxide is done electrochemical capacitor electrode material and is had the life-span long (density of manganese oxide is 3.79 g/cm with the density height
3) advantage.Manganese oxide mainly contains as the problem that super capacitor material faces: (1) conductivity is lower, power-performance is poor; (2) the material actual specific capacity is also far below theoretical value, so the space that has greatly improved.Be expected to make manganese oxide material charge and discharge process intermediate ion body to move distance mutually through material nanoization and shorten, active material utilization improves, and then improves its specific capacity and high rate performance.
At present, the method for preparing manganese oxide mainly contains: hydro thermal method, sol-gel process, template, phonochemistry method, oxidation-reduction method and high-temperature decomposition etc.Although the researcher has made the manganese oxide nano material of various patterns through above method, yet because these material porositys are low, do not have flourishing electron conduction path, performance is not high.
Summary of the invention
The object of the present invention is to provide the method for a kind of multi-hole casting carbon/manganese oxide nano composite material.The present invention is a raw material with multi-hole casting carbon and manganese containing materials, through ultrasonic manganese containing materials is reduced, and prepares through heat treatment more afterwards.Prepared multi-hole casting carbon/manganese oxide composite material has high specific area and electronic conductivity.Electrochemical property test shows that the multi-hole casting carbon/manganese oxide nano composite material of preparation has higher ratio electric capacity, good multiplying power property and cyclical stability, is the ideal electrode material as ultracapacitor.
A kind of multi-hole casting carbon/manganese oxide nano composite material, material component are in mass percent: the content of multi-hole casting carbon accounts for 2 ~ 98 %, and the content of manganese oxide accounts for 98 ~ 2 %; The aperture of multi-hole casting carbon is in 5 nanometers to 10 micron, and the particle diameter of this multi-hole casting carbon/manganese oxide nano composite material is between 5 nanometers to 10 millimeter; Density is at 1 ~ 4 g/cm
3, total specific area is at 50 ~ 1500g/cm
2
Processing step is:
Multi-hole casting carbon (granule size: 5 nanometers to 10 millimeter; Aperture: 5 nanometers to 10 micron) adds the manganese containing materials (potassium permanganate of certain mass concentration (1%～80%); Manganese sulfate; Manganese acetate; Manganese chloride; In the manganese carbonate one or several) in the aqueous solution; Wherein the ratio of multi-hole casting carbon and manganese containing materials is 1:100～100:1; Uniform temperature (0～80 ℃) sonicated a period of time (5 minutes～24 hours) in the ultrasonic reactor of certain power (50 ~ 2000 watts every square centimeter) and frequency (10 ~ 200 KHz) then; Then through filtering; Washing; Dry; At last at inert gas (argon gas; Nitrogen; One of in the helium or several mixing) protection is down uniform temperature (50 ℃～400 ℃) roasting 1～4 hour, just obtains multi-hole casting carbon/manganese oxide nano composite material.
Advantage or good effect
Adopt the multi-hole casting carbon/manganese oxide nano composite material of this method preparation, have the following advantages: (i) selected raw material economics environmental protection, inexpensive; (ii) this multi-hole casting carbon/manganese oxide nano composite material has higher specific surface area and electronic conductivity, thereby makes device can have good capacity and high rate performance; (iv) preparation technology is simple, and cost is low, is suitable for suitability for industrialized production.
Description of drawings
The typical scan electromicroscopic photograph of Fig. 1 multi-hole casting carbon.
The typical scan electromicroscopic photograph of Fig. 2 multi-hole casting carbon/manganese oxide nano composite material.
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Embodiment
Below in conjunction with embodiment the present invention is further specified, but does not limit protection scope of the present invention:
Embodiment 1:
Multi-hole casting carbon (granularity: 1 micron; Average pore size: 80 nanometers) adding mass concentration is in 20% the potassium permanganate solution; Wherein the part by weight of multi-hole casting carbon and potassium permanganate is 1:20; Being 100 watts every square centimeter at power then is to be 25 ℃ of ultrasonic reactions 1 hour in temperature in the ultrasonic reactor of 20 KHz with frequency; Then through filtration, washing, drying; At last under nitrogen protection 120 ℃ of roastings 2 hours, just obtain multi-hole casting carbon/manganese oxide nano composite material.The pattern of this multi-hole casting carbon is seen Fig. 1, and the stereoscan photograph of multi-hole casting carbon/manganese oxide nano composite material is seen Fig. 2, and manganese oxide accounts for 70% of total weight in this composite material, and specific area is 800 m
2/ g, density is 3 g/cm
3Is this composite material and acetylene black, polytetrafluoroethylene that 8:1:1 is mixed with electrode slice according to weight ratio.Test ultracapacitor performance in 1M sodium sulphate, when this material was used as ultracapacitor, when 10 millivolts/second sweep speed, the ratio electric capacity in 1M sodium sulphate was the every grams of 285 faraday.At organic system electrolyte (1M Et
4NBF
4/ PC) in when test, be the every grams of 204 faraday than electric capacity.1500 capacity of circulation remain on more than 96.8% in the 1M sodium sulphate, and 1500 capacity of organic system circulate electrolyte remain on more than 94.7%.
Embodiment 2:
Multi-hole casting carbon (granularity: 20 microns; Average pore size: 10 nanometers) adding mass concentration is in 70% the potassium permanganate solution; Wherein the part by weight of multi-hole casting carbon and potassium permanganate is 1:10; Being 1 kilowatt every square centimeter at power then is to be 55 ℃ of ultrasonic reactions 5 hours in temperature in the ultrasonic reactor of 40 KHz with frequency; Then through filtration, washing, drying; At last under argon shield 200 ℃ of roastings 3 hours, just obtain multi-hole casting carbon/manganese oxide nano composite material.Manganese oxide accounts for 40% of total weight in this composite material, and specific area is 320 m
2/ g, density is 2.7g/cm
3Is this composite material and acetylene black, polytetrafluoroethylene that 8:1:1 is mixed with electrode slice according to weight ratio.When this material is used as ultracapacitor, test ultracapacitor performance in 1M sodium sulphate, when 10 millivolts/second sweep speed, the ratio electric capacity in 1M sodium sulphate is the every grams of 240 faraday, at organic system electrolyte (1M Et
4NBF
4/ PC) in when test, be the every grams of 160 faraday than electric capacity.Circulation is 50,000 times in the 1M sodium sulphate, and capacity remains on more than 98%; 1500 capacity of organic system circulate electrolyte remain on more than 93.4%.
Embodiment 3:
Multi-hole casting carbon (granularity: 5 millimeters; The aperture: 30 nanometers) adding mass concentration is in 40% the potassium permanganate solution; Wherein the ratio of multi-hole casting carbon and potassium permanganate is 1:5; Being 800 watts every square centimeter at power then is to be 60 ℃ of ultrasonic reactions 10 hours in temperature in the ultrasonic reactor of 20 KHz with frequency; Then through filtration, washing, drying; At last under nitrogen protection 120 ℃ of roastings 10 hours, just obtain multi-hole casting carbon/manganese oxide nano composite material.Manganese oxide accounts for 30% of total weight in this composite material, and specific area is 690 m
2/ g, density is 2.95g/cm
3Is this composite material and acetylene black, polytetrafluoroethylene that 9:0.5:0.5 is mixed with electrode slice according to weight ratio.When this material was used as ultracapacitor, when 10 millivolts/second sweep speed, the ratio electric capacity in 1M sodium sulphate was the every grams of 228 faraday, at organic system electrolyte (1M Et
4NBF
4/ AN) in when test, be the every grams of 147 faraday than electric capacity.Circulation is 50,000 times in the 1M sodium sulphate, and capacity remains on 97%, organic system circulate electrolyte 50,000 times, and capacity remains on 96%.
Embodiment 4:
Multi-hole casting carbon (granularity: 8 millimeters; The aperture: 10 nanometers) adding mass concentration is in 70% the high manganese material aqueous solution; Wherein manganese containing materials is potassium permanganate and manganese sulfate; Mol ratio is 2:3; The ratio of multi-hole casting carbon and manganese containing materials system is 1:50; Being 2000 watts every square centimeter at power then is to be 10 ℃ of ultrasonic reactions 4 hours in temperature in the ultrasonic reactor of 60 KHz with frequency; Then through filtration, washing, drying; At last under nitrogen protection 190 ℃ of roastings 6 hours, just obtain multi-hole casting carbon/manganese oxide nano composite material.Manganese oxide accounts for 81% of total weight in this composite material, and specific area is 125m
2/ g, density is 3.17g/cm
3When this material was used as ultracapacitor, when 10 millivolts/second sweep speed, the ratio electric capacity in 1M sodium sulphate was the every grams of 268 faraday, at organic system electrolyte (1M Et
4NBF
4/ PC) in when test, be the every grams of 156 faraday than electric capacity.Circulation is 50,000 times in the aqueous electrolyte, and capacity remains on 98%; Organic system circulate electrolyte 50,000 times, capacity remains on 96%.
Embodiment 5:
Multi-hole casting carbon (granularity: 8 millimeters; The aperture: 10 nanometers) adding mass concentration is in 70% the high manganese material aqueous solution; Wherein manganese containing materials is potassium permanganate and manganese chloride; Mol ratio is 1:2; The ratio of multi-hole casting carbon and manganese containing materials system is 1:50; Being 2000 watts every square centimeter at power then is to be 10 ℃ of ultrasonic reactions 4 hours in temperature in the ultrasonic reactor of 60 KHz with frequency; Then through filtration, washing, drying; At last under nitrogen protection 150 ℃ of roastings 6 hours, just obtain multi-hole casting carbon/manganese oxide nano composite material.Manganese oxide accounts for 70% of total weight in this composite material, and specific area is 140m
2/ g, density is 2.9g/cm
3When this material was used as ultracapacitor, when 10 millivolts/second sweep speed, the ratio electric capacity in 1M sodium sulphate was the every grams of 240 faraday, at organic system electrolyte (1M Et
4NBF
4/ PC) in when test, be the every grams of 155 faraday than electric capacity.1M sodium sulphate circulates 50,000 times, and capacity remains on 98%, organic system electrolyte (1M Et
4NBF
4/ PC) circulating 50,000 times, capacity remains on 95%.
Claims (3)
1. multi-hole casting carbon/manganese oxide nano composite material is characterized by: component is in mass percent: the content of multi-hole casting carbon accounts for 2 ~ 98 %, and the content of manganese oxide accounts for 98 ~ 2 %; The aperture of multi-hole casting carbon is in 5 nanometers to 10 micron, and the particle diameter of this multi-hole casting carbon/manganese oxide nano composite material is between 5 nanometers to 10 millimeter; Density is at 1 ~ 4 g/cm
3, total specific area is at 50 ~ 1500g/cm
2
2. method for preparing multi-hole casting carbon as claimed in claim 1/manganese oxide nano composite material, it is characterized in that: processing step is:
Is granule size 5 nanometers to 10 millimeter; The aperture is that to add mass concentration be in 1% ~ 80% the manganese containing materials aqueous solution to 5 nanometers to 10 micron multi-hole casting carbon; Hydrous material is a potassium permanganate; Manganese sulfate; Manganese acetate; Manganese chloride; In the manganese carbonate one or several; Wherein the ratio of multi-hole casting carbon and manganese containing materials is 1:100 ~ 100:1; Being 50 ~ 2000 watts every square centimeter at power then is in the ultrasonic reactor of 10 ~ 200 KHz with frequency; 0 ~ 80 ℃ of following sonicated 5 minutes ~ 24 hours; Then through filtering; Washing; Dry; At last under inert gas shielding 50 ℃ ~ 400 ℃ roastings 1 ~ 4 hour; Just obtain multi-hole casting carbon/manganese oxide nano composite material, inert gas is an argon gas; Nitrogen; One of in the helium or several mixing.
3. like the multi-hole casting carbon/manganese oxide nano composite material of method preparation as described in the claim 2, it is characterized in that described multi-hole casting carbon/manganese oxide nano composite material is directly as the electrode material of ultracapacitor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104134548A (en) * | 2014-07-09 | 2014-11-05 | 上海应用技术学院 | Porous composite material of manganese dioxide and carbon and preparation method thereof |
| CN106206061A (en) * | 2016-07-15 | 2016-12-07 | 上海应用技术学院 | A kind of preparation method and applications of mesoporous manganese oxide/carbon composite nano-material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1809516A (en) * | 2003-06-20 | 2006-07-26 | 松下电器产业株式会社 | Porous body and its production method |
| CN101038816A (en) * | 2007-04-20 | 2007-09-19 | 哈尔滨工程大学 | Method for preparing porous carbon/nano metal oxide composite material |
| CN101819883A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for preparing mesoporous carbon composite material used for supercapacitor electrode |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1809516A (en) * | 2003-06-20 | 2006-07-26 | 松下电器产业株式会社 | Porous body and its production method |
| CN101038816A (en) * | 2007-04-20 | 2007-09-19 | 哈尔滨工程大学 | Method for preparing porous carbon/nano metal oxide composite material |
| CN101819883A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for preparing mesoporous carbon composite material used for supercapacitor electrode |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104134548A (en) * | 2014-07-09 | 2014-11-05 | 上海应用技术学院 | Porous composite material of manganese dioxide and carbon and preparation method thereof |
| CN104134548B (en) * | 2014-07-09 | 2017-02-15 | 上海应用技术学院 | Porous composite material of manganese dioxide and carbon and preparation method thereof |
| CN106206061A (en) * | 2016-07-15 | 2016-12-07 | 上海应用技术学院 | A kind of preparation method and applications of mesoporous manganese oxide/carbon composite nano-material |
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