CN103127941A - Mn-Co/graphene catalyst used for lithium-air battery and preparation method - Google Patents
Mn-Co/graphene catalyst used for lithium-air battery and preparation method Download PDFInfo
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- CN103127941A CN103127941A CN2013100668600A CN201310066860A CN103127941A CN 103127941 A CN103127941 A CN 103127941A CN 2013100668600 A CN2013100668600 A CN 2013100668600A CN 201310066860 A CN201310066860 A CN 201310066860A CN 103127941 A CN103127941 A CN 103127941A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a Mn-Co/graphene catalyst used for a lithium-air battery and a preparation method. According to the invention, a carrier of the catalyst is graphene, and an active component is a Mn-based oxide doped with cobaltous oxide. The method for preparing the catalyst comprises the following steps: immersing the graphene in ammonia water, stirring evenly by ultrasound, and adding manganese salt and cobalt salt, then adding an aqueous alkali to regulate the pH value, continuously stirring by ultrasound; and washing after finishing the reaction and drying. The Mn-Co/graphene catalyst used for the lithium-air battery can present good catalytic activity.
Description
Technical field
The invention belongs to the electrochemical catalysis field, relate in particular to a kind of Mn-Co/ graphen catalyst and preparation method for lithium-air battery.
Background technology
Lithium-air battery has that capacity is large, specific energy is high, stable operating voltage, cheap and advantages of environment protection, is a kind of electrochmical power source with great market prospect.Along with the development of Modern Manufacturing Technology, lithium-air battery will be used widely in fields such as portable computer, electronic installation, remote control equipment and military communication devices.The Focal point and difficult point of studying and develop at present the high power battery that is applicable to the electric vehicle electrical source of power.
Air electrode is a kind of gas-diffusion electrode, and its one side contacts with electrolyte, and one side contacts with airborne oxygen, forms the stable state of a kind of three-phase at catalyst surface.In battery discharge procedure, air electrode is as negative electrode, and oxygen diffuses into electrode interior along electrode surface, and the reduction reaction occurs under the effect of catalyst.
Air electrode is chief component parts in lithium-air battery, and the quality of its performance has determined the size of battery power output.The catalytic activity of air electrode catalyst plays a part crucial in the use of battery, improves the catalytic activity of air electrode catalyst, means under certain working current density, take air electrode as anodal lithium-air battery, higher output potential is arranged.Therefore, need the high performance catalyst for air electrode of exploitation, accelerate applying of lithium-air battery.
Summary of the invention
The objective of the invention is a kind of Mn-Co/ graphen catalyst and preparation method for lithium-air battery, this catalyst hydrogen reduction activity is high, easy to prepare, cheap and easy to get.
For achieving the above object, the present invention takes following design:
A kind of Mn-Co/ graphen catalyst for lithium-air battery, its carrier is Graphene, active component is the Mn base oxide of cobalt oxide of having adulterated.
A kind of Mn-Co/ graphen catalyst for lithium-air battery take Graphene as carrier, adds manganese salt, then adds cobalt salt, after reaction under the aqueous slkali environment, then forms through deionized water washing, the final drying of removal foreign ion; Wherein, the percentage by weight of main material composition is: manganese salt 5～40%, and cobalt salt 0～30%, surplus is Graphene.
Described manganese salt is MnSO
4, Mn (NO
3)
2Perhaps KMnO
4Described cobalt salt is CoSO
4, Co (NO
3)
2Perhaps CoCl
2
The preparation of described Graphene is: under 0 ℃ of ice bath, be distributed in 20～25ml concentrated sulfuric acid by every 0.015～0.12g graphite powder, add KMnO under stirring
4, institute adds KMnO
4Quality be 3～4 times of graphite powder, stirred 30-60 minute, temperature rises to 30～35 ℃ of left and right, adds the 46ml deionized water, stirs 20～30 minutes, adds the H of 10ml mass concentration 30%
2O
2, stirred 5～10 minutes, through centrifugation, with obtaining graphene oxide after mass concentration 5%HCl solution, deionized water and acetone cyclic washing.
A kind of Mn-Co/ graphen catalyst for lithium-air battery, the preparation method is as follows: at first Graphene is immersed in ammoniacal liquor, after ultrasonic agitation is even, add in proportion manganese salt, add in proportion again cobalt salt, then add aqueous slkali to regulate the pH value 8～14, continued ultrasonic agitation 2～10 hours; After reaction is completed, use deionized water Xian Di, remove foreign ion, then put into air dry oven, 60～150 ℃ of oven dry, described aqueous slkali is NaOH or KOH solution.
The ratio of described Graphene and ammoniacal liquor is 1:5～1:500.
Advantage of the present invention is:
L, the present invention prepare the material that air electrode uses with catalyst, for cheap metallic salt and ammoniacal liquor etc., greatly reduce production cost;
2, have the characteristics such as high specific area, superpower mechanical property, excellent conduction and heat conduction due to graphene nanometer sheet, be conducive to electronics transmission in electrochemical electrode reaction and catalytic reaction process and the stability of electrode, the chemical property of reinforced composite.
The specific embodiment
Embodiment 1
The 30g Graphene is immersed in ammoniacal liquor, and the ratio of Graphene and ammoniacal liquor is 1:5, after ultrasonic agitation is even, adds 12.1gMnSO
4, add 7.9gCoCl
2, then adding concentration is that 0.05M NaOH solution adjusting pH value is 8, continues ultrasonic agitation 4.5 hours; After reaction is completed, with the deionized water washing, remove foreign ion, then put into air dry oven, 100 ℃ of oven dry.Wherein, the percentage by weight of main material composition is: manganese salt 24.2%, and cobalt salt 15.8%, surplus is Graphene.
Embodiment 2
The 25g Graphene is immersed in ammoniacal liquor, and the ratio of Graphene and ammoniacal liquor is 1:200, after ultrasonic agitation is even, adds 13.2g Mn (NO
3)
2, add 4g CoCl
2, then adding concentration is that 0.05M NaOH solution adjusting pH value is 11, continues ultrasonic agitation 5 hours; After reaction is completed, with the deionized water washing, remove foreign ion, then put into air dry oven, 90 ℃ of oven dry.Wherein, the percentage by weight of main material composition is: manganese salt 31.3%, and cobalt salt 9.5%, surplus is Graphene.
Embodiment 3
The 18g Graphene is immersed in ammoniacal liquor, and the ratio of Graphene and ammoniacal liquor is 1:100, after ultrasonic agitation is even, adds 9.6g KMnO
4, add 6.3g Co (NO
3)
2, then adding concentration is that 0.05M NaOH solution adjusting pH value is 9, continues ultrasonic agitation 4.5 hours; After reaction is completed, with the deionized water washing, remove foreign ion, then put into air dry oven, 100 ℃ of oven dry.Wherein, the percentage by weight of main material composition is: manganese salt 28.3%, and cobalt salt 18.6%, surplus is Graphene.
Embodiment 4
The 30g Graphene is immersed in ammoniacal liquor, and the ratio of Graphene and ammoniacal liquor is 1:50, after ultrasonic agitation is even, adds 4.3g MnSO
4, add 2.1g CoCl
2, then adding concentration is that 0.05M NaOH solution adjusting pH value is 8, continues ultrasonic agitation 5 hours; After reaction is completed, with the deionized water washing, remove foreign ion, then put into air dry oven, 80 ℃ of oven dry.Wherein, the percentage by weight of main material composition is: manganese salt 11.8%, and cobalt salt 5.8%, surplus is Graphene.
Claims (6)
1. a Mn-Co/ graphen catalyst that is used for lithium-air battery, is characterized in that, carrier is Graphene, and active component is the Mn base oxide of cobalt oxide of having adulterated.
2. a kind of Mn-Co/ graphen catalyst for lithium-air battery according to claim 1, is characterized in that, take Graphene as carrier, add manganese salt, add again cobalt salt, after reaction under the aqueous slkali environment, then form through deionized water washing, the final drying of removal foreign ion; Wherein, the percentage by weight of main material composition is: manganese salt 5～40%, and cobalt salt 0～30%, surplus is Graphene.
3. a kind of Mn-Co/ graphen catalyst for lithium-air battery according to claim 2, is characterized in that, described manganese salt is MnSO
4, Mn (NO
3)
2Perhaps KMnO
4Described cobalt salt is CoSO
4, Co (NO
3)
2Perhaps CoCl
2
4. a kind of Mn-Co/ graphen catalyst for lithium-air battery according to claim 1 and 2, it is characterized in that, the preparation of described Graphene is: under 0 ℃ of ice bath, be distributed in 20～25ml concentrated sulfuric acid by every 0.015～0.12g graphite powder, add KMnO under stirring
4, institute adds KMnO
4Quality be 3～4 times of graphite powder, stirred 30-60 minute, temperature rises to 30～35 ℃ of left and right, adds the 46ml deionized water, stirs 20～30 minutes, adds the H of 10ml mass concentration 30%
2O
2, stirred 5～10 minutes, through centrifugation, with obtaining graphene oxide after mass concentration 5%HCl solution, deionized water and acetone cyclic washing.
5. method for preparing claim 1 or 2 described catalyst, it is characterized in that, method is as follows: at first Graphene is immersed in ammoniacal liquor, after ultrasonic agitation is even, add in proportion manganese salt, add in proportion again cobalt salt, then add aqueous slkali to regulate the pH value 8～14, continued ultrasonic agitation 2～10 hours; After reaction is completed, use deionized water Xian Di, remove foreign ion, then put into air dry oven, 60～150 ℃ of oven dry, described aqueous slkali is NaOH or KOH solution.
6. according to claim 2 or 5 described a kind of Mn-Co/ graphen catalysts for lithium-air battery, is characterized in that, the ratio of described Graphene and ammoniacal liquor is 1:5～1:500.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624191A (en) * | 2013-11-11 | 2015-05-20 | 中国科学院大连化学物理研究所 | CoO/C catalyst and preparation method thereof |
| CN105576261A (en) * | 2015-12-22 | 2016-05-11 | 北京化工大学常州先进材料研究院 | Mn-Ni/graphene catalyst for lithium-air batteries and preparation method |
| CN108172411A (en) * | 2018-01-16 | 2018-06-15 | 武汉低维材料研究院有限公司 | A kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material |
| CN108198700A (en) * | 2018-01-16 | 2018-06-22 | 武汉低维材料研究院有限公司 | A kind of preparation method and applications of graphene-carbon nano tube/cobalt manganese alloy oxide nano-slice compound |
| CN110252331A (en) * | 2019-06-20 | 2019-09-20 | 宁波智通环保科技有限公司 | A kind of room temperature is except ozone catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142540A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Lithium ion battery electrode made of graphene/SnS2 composite nanometer material and preparation method thereof |
-
2013
- 2013-03-04 CN CN2013100668600A patent/CN103127941A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142540A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Lithium ion battery electrode made of graphene/SnS2 composite nanometer material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| HAILIANG WANG ET AL: "Rechargeable Li–O2 batteries with a covalently coupled MnCo2O4–grapheme hybrid as an oxygen cathode catalyst", 《ENERGY & ENVIRONMENTAL SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104624191A (en) * | 2013-11-11 | 2015-05-20 | 中国科学院大连化学物理研究所 | CoO/C catalyst and preparation method thereof |
| CN105576261A (en) * | 2015-12-22 | 2016-05-11 | 北京化工大学常州先进材料研究院 | Mn-Ni/graphene catalyst for lithium-air batteries and preparation method |
| CN108172411A (en) * | 2018-01-16 | 2018-06-15 | 武汉低维材料研究院有限公司 | A kind of preparation method of cobalt manganese alloy oxide-sulfur and nitrogen co-doped graphene nanocomposite material |
| CN108198700A (en) * | 2018-01-16 | 2018-06-22 | 武汉低维材料研究院有限公司 | A kind of preparation method and applications of graphene-carbon nano tube/cobalt manganese alloy oxide nano-slice compound |
| CN110252331A (en) * | 2019-06-20 | 2019-09-20 | 宁波智通环保科技有限公司 | A kind of room temperature is except ozone catalyst and preparation method thereof |
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Application publication date: 20130605 |