CN103165912A - Catalytic agent for lithium-air battery cathode and preparation method - Google Patents
Catalytic agent for lithium-air battery cathode and preparation method Download PDFInfo
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- CN103165912A CN103165912A CN2013100637886A CN201310063788A CN103165912A CN 103165912 A CN103165912 A CN 103165912A CN 2013100637886 A CN2013100637886 A CN 2013100637886A CN 201310063788 A CN201310063788 A CN 201310063788A CN 103165912 A CN103165912 A CN 103165912A
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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 catalytic agent for a lithium-air battery cathode and a preparation method. The catalytic agent comprises a nano-manganese dioxide active component and a metal-organic frameworks (MOFs) carrier, and a molar ratio of the MOFs to the nano-manganese oxide is 5: 1-30: 1. The nano-manganese oxide is deposited on the surface of the MOFs material through a hydrothermal method or a redox process, so that the catalytic agent is prepared to be used on the lithium-air battery cathode. The catalytic agent has very good catalytic activity, the overvoltage of a battery is reduced, and therefore the charge-discharge efficiency of the lithium-air battery is improved. In addition, the preparation method of the catalytic agent is simple, practicable and pollution-free. Complex and strict reaction conditions do not need to be adopted.
Description
Technical field
The invention belongs to the lithium-air battery field, be specifically related to a kind of catalyst for the lithium-air battery negative electrode and preparation method.
Background technology
In theory, because airborne oxygen is not limited as the lithium-air battery anode reactant, the capacity of lithium-air battery only depends on lithium electrode, its specific energy is that 5.21kWh/kg(comprises oxygen quality), or 11.14kWh/kg(does not comprise oxygen quality), be more than 10 times of present lithium ion battery.In addition, with respect to other metal-air battery, lithium-air battery has higher specific energy, and lithium-air battery is free of contamination.Therefore in recent years, lithium-air battery causes more and more researchers' concern.But the reaction of the oxygen reduction of lithium-air battery positive pole is slow reaction, due to the restriction of catalyst performance at present, there is overvoltage in battery in charge and discharge process, caused very large energy loss, greatly reduce the battery Rechargeability, thereby reduced charge and discharge cycles efficient and the cycle performance of battery, be difficult to commercial applications.Therefore in the urgent need to seeking high performance catalyst, to accelerate the oxygen reduction reaction speed, reduce the battery overvoltage, improve charge and discharge cycles efficient and cycle performance.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can improve the oxygen reduction reaction speed, reduce overvoltage, improve the catalyst of lithium-air battery performance, a kind of with low cost, simple to operate, the free of contamination preparation method of above-mentioned catalyst also are provided simultaneously, not enough with the customer service prior art.
The objective of the invention is to solve by the following technical programs:
A kind of catalyst for the lithium-air battery negative electrode comprises nano-manganese dioxide active component and metallic organic framework (MOFs), and wherein, the mol ratio of MOFs and nano-manganese dioxide is 5:1～30:1.
A kind of preparation method of the catalyst for the lithium-air battery negative electrode comprises the following steps:
Get potassium permanganate and reducing agent, add distilled water to make its dissolving, add MOFs, add in autoclave after stirring 10～30min, at 140～180 ℃ of lower hydro-thermal reaction 8～72h, be cooled to room temperature after hydro-thermal reaction, filtering, is catalyst with lower sediment after 50～150 ℃ of drying 10～24h.
In above-mentioned preparation process, material molar ratio is potassium permanganate: reducing agent: distilled water: MOFs=1:1:1:5～1:1:2:30.
In above-mentioned preparation process, reducing agent is the hydrochloric acid of ammonium chloride, manganese sulfate or 1.0～5.0mol/L.
Another kind of the present invention comprises the following steps for the preparation of the method for the catalyst of lithium-air battery negative electrode:
(1) MOFs is joined in distilled water, in 50～80 ℃ of stirring 20～60min, wherein the mass ratio of distilled water and MOFs is 50:1～200:1;
(2) take MnCl according to mol ratio 1:2～4:2
24H
2O and KMnO
4, join in the hot water of 50～80 ℃;
(3) dropwise the solution that obtains in described step (2) is added in the resulting solution of step (1), stir 1～2h under 50～80 ℃, centrifugal, filter, and wash with deionized water, the precipitation that then will filter out is placed in drying box at 70～150 ℃ of drying 8～10h, namely gets catalyst.
In above-mentioned preparation method, the MnCl in step (2)
24H
2O replaces with manganese sulfate.
Compared with prior art, have the specific area of superelevation due to MOFs, with manganese dioxide with load on the MOFs material, both increased the specific area of electrode, improve again the catalytic efficiency of catalyst, reduced widely overvoltage, improved the performance of lithium-air battery.The advantages such as simultaneously, the preparation method of catalyst has simple, need not to adopt complicated harsh reaction condition, and exploitativeness is strong, and is pollution-free.
Embodiment
Embodiment 1
Add 0.5mmol KMnO in the 50mL reactor
4, 0.5mmol NH
4C1 and 30mL deionized water, and 10mgMOFs stir 10min, then are placed in baking oven, react 8h under 140 ℃, then carry out centrifugal, filtration, then use deionized water and absolute ethyl alcohol cyclic washing repeatedly, at 80 ℃ of dry 12h, get catalyst sample at last.
Embodiment 2
Add 0.7mmol KMnO in the 50mL reactor
4, 0.7mmol MnSO
4With the 35mL deionized water, and 20mgMOFs, stir 10min, then be placed in baking oven, react 24h under 180 ℃, then carry out centrifugal, filtration, then use deionized water and absolute ethyl alcohol cyclic washing repeatedly, at 150 ℃ of dry 12h, get catalyst sample at last.
Embodiment 3
Add 0.9mmol KMnO in the 50mL reactor
4, 0.9mmol HC1 and 35mL deionized water, and 37mgMOFs stir 10min, then be placed in baking oven, react 72h under 160 ℃, then carry out centrifugal, filtration, use again deionized water and absolute ethyl alcohol cyclic washing repeatedly, at 130 ℃ of dry 24h, get catalyst sample at last.
Embodiment 4
150mL distilled water is added in closed container, be heated to 50 ℃, add 0.5g MOFs, in 50 ℃ of stirring 20min, get solution 1, with 1.4g MnCl
2H
2O and 3.16g KMnO
4(both mol ratio is 1:2) is dissolved in 25mL hot water, gets solution 2; Solution 2 is dropwise added in solution 1, and 70 ℃ are stirred 1h, filter, and the deionized water washing, then 70 ℃ of dry 8h, get catalyst sample.
Embodiment 5
150mL distilled water is added in closed container, be heated to 80 ℃, add 0.5g MOFs, in 80 ℃ of stirring 20min, get solution 1, with 5.1g MnSO
4H
2O and 3.16g KMnO
4(both mol ratio is 3:2) is dissolved in 25mL hot water, gets solution 2; Solution 2 is dropwise added in solution 1, and 70 ℃ are stirred 1h, filter, and the deionized water washing, then 70 ℃ of dry 10h, get catalyst sample.
Claims (5)
1. a catalyst that is used for the lithium-air battery negative electrode, is characterized in that, this catalyst comprises nano-manganese dioxide active component and metallic organic framework compound (MOFs) carrier, and the mol ratio of MOFs and nano-manganese dioxide is 5:1～30:1.
2. a catalyst that is used for according to claim 1 the lithium-air battery negative electrode, is characterized in that, the preparation method of catalyst is as follows:
Get potassium permanganate and reducing agent, add distilled water to make its dissolving, add MOFs, add in autoclave after stirring 10～30min, at 140～180 ℃ of lower hydro-thermal reaction 8～72h, be cooled to room temperature after hydro-thermal reaction, filter, lower sediment is namely got catalyst after 50～150 ℃ of drying 10～24h; Wherein, material molar ratio is potassium permanganate: reducing agent: distilled water: MOFs=1:1:1:5～1:1:2:30.
3. a kind of catalyst and preparation method for the lithium-air battery negative electrode according to claim 2, is characterized in that, described reducing agent is the hydrochloric acid of ammonium chloride, manganese sulfate or 1.0～5.0mol/L.
4. a catalyst that is used for according to claim 1 the lithium-air battery negative electrode, is characterized in that, the preparation method of catalyst comprises the following steps:
(1) MOFs is joined in distilled water, in 50～80 ℃ of stirring 20～60min, wherein the mass ratio of distilled water and MOFs is 50:1～200:1;
(2) take MnCl according to mol ratio 1:2～4:2
24H
2O and KMnO
4, join in the hot water of 50～80 ℃;
(3) dropwise the solution that obtains in described step (2) is added in the resulting solution of step (1), stir 1～2h under 50～80 ℃, centrifugal, filter, and wash with deionized water, the precipitation that then will filter out is placed in drying box at 70～150 ℃ of drying 8～10h, namely gets catalyst.
5. a kind of catalyst and preparation method for the lithium-air battery negative electrode according to claim 4, is characterized in that the MnCl in described step (2)
24H
2O replaces with manganese sulfate.
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Cited By (7)
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|---|---|---|---|---|
| US20160016158A1 (en) * | 2014-07-15 | 2016-01-21 | Sonbinh T. Nguyen | Catalyst Composition and Process for Preparing Olefin Oxides |
| CN106334552A (en) * | 2016-09-30 | 2017-01-18 | 上海理工大学 | MnOx catalyst, preparation method thereof and application thereof to prevention and control of environmental pollution |
| CN106423293A (en) * | 2016-09-24 | 2017-02-22 | 上海大学 | Preparation method of catalytic composite material Mn3O4/ZIF-8 (Zeolite Imidazate Framework-8) for activating PMS (Potassium Monopersulfate) |
| CN107123553A (en) * | 2017-01-10 | 2017-09-01 | 新疆大学 | One kind prepares Mn using MOF templates3O4The method of hollow micro-nano cubic block |
| CN107316756A (en) * | 2017-06-29 | 2017-11-03 | 扬州大学 | A kind of preparation method of cladding Cu MOF ultra-thin nano material of manganese dioxide |
| CN109592715A (en) * | 2018-12-21 | 2019-04-09 | 陕西师范大学 | A method of using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide |
| CN110364693A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | Nano three-dimensional conductive framework/MnO 2 Preparation method of composite structure material and application of composite structure material in zinc battery anode |
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| CN102664277A (en) * | 2012-05-18 | 2012-09-12 | 东南大学 | Composite material used as lithium air battery positive electrode and preparation method thereof |
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| CN102751494A (en) * | 2012-07-09 | 2012-10-24 | 广州市香港科大霍英东研究院 | Preparation method of novel porous skeleton MIL-101(Cr)@S/graphene composite material for cathode of lithium sulfur battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160016158A1 (en) * | 2014-07-15 | 2016-01-21 | Sonbinh T. Nguyen | Catalyst Composition and Process for Preparing Olefin Oxides |
| US9943839B2 (en) * | 2014-07-15 | 2018-04-17 | Northwestern University | Catalyst composition and process for preparing olefin oxides |
| US10525455B2 (en) | 2014-07-15 | 2020-01-07 | Northwestern University | Catalyst composition and process for preparing olefin oxides |
| CN106423293A (en) * | 2016-09-24 | 2017-02-22 | 上海大学 | Preparation method of catalytic composite material Mn3O4/ZIF-8 (Zeolite Imidazate Framework-8) for activating PMS (Potassium Monopersulfate) |
| CN106423293B (en) * | 2016-09-24 | 2018-12-07 | 上海大学 | A kind of catalytic composite materials Mn activating PMS3O4The preparation method of/ZIF-8 |
| CN106334552A (en) * | 2016-09-30 | 2017-01-18 | 上海理工大学 | MnOx catalyst, preparation method thereof and application thereof to prevention and control of environmental pollution |
| CN107123553A (en) * | 2017-01-10 | 2017-09-01 | 新疆大学 | One kind prepares Mn using MOF templates3O4The method of hollow micro-nano cubic block |
| CN107123553B (en) * | 2017-01-10 | 2019-03-05 | 新疆大学 | It is a kind of to prepare Mn using MOF template3O4The method of hollow micro-nano cubic block |
| CN107316756A (en) * | 2017-06-29 | 2017-11-03 | 扬州大学 | A kind of preparation method of cladding Cu MOF ultra-thin nano material of manganese dioxide |
| CN110364693A (en) * | 2018-04-10 | 2019-10-22 | 中国科学院上海硅酸盐研究所 | Nano three-dimensional conductive framework/MnO 2 Preparation method of composite structure material and application of composite structure material in zinc battery anode |
| CN110364693B (en) * | 2018-04-10 | 2020-11-20 | 浙江浙能中科储能科技有限公司 | Nano three-dimensional conductive framework/MnO 2 Preparation method of composite structure material and application of composite structure material in zinc battery anode |
| CN109592715A (en) * | 2018-12-21 | 2019-04-09 | 陕西师范大学 | A method of using two hydration terephthalic acid (TPA) manganese as presoma controllable preparation different structure manganese oxide |
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Application publication date: 20130619 |