CN103151532A - Novel air electrode for metal-air battery - Google Patents
Novel air electrode for metal-air battery Download PDFInfo
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- CN103151532A CN103151532A CN201310066291XA CN201310066291A CN103151532A CN 103151532 A CN103151532 A CN 103151532A CN 201310066291X A CN201310066291X A CN 201310066291XA CN 201310066291 A CN201310066291 A CN 201310066291A CN 103151532 A CN103151532 A CN 103151532A
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- air electrode
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- air cell
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a novel air electrode for a metal-air battery. The air electrode is obtained by pressing a catalyst layer, a diffusion layer and a current collecting layer, wherein the catalyst in the catalyst layer is TiO2/graphene and is prepared by using the following method: treating graphene by 10% by volume dilute nitric acid; filtering; washing for a plurality of times by using distilled water; drying; carrying out hydrolysis reaction on the dried graphene and a titanic chloride solution at 0-10 DEG C, wherein the mass ratio of the titanic chloride solution is 1-10 times that of the graphene; roasting the reaction product at 300-900 DEG C; cooling the roasted product to room temperature; and grinding the cooled product to obtain the TiO2/graphene. Compared with the prior art, the air electrode disclosed by the invention is simple in preparation of the used catalyst and low in cost; and with the application of the catalyst, the current density of the air electrode is improved well.
Description
Technical field
The present invention relates to air electrode, particularly for the air electrode of metal-air cell.
Background technology
In recent years, along with the development of economy, must cause the exhaustion of petroleum resources, the aggravation of global warming and environmental pollution.New forms of energy, oneself becomes very necessary problem the comprehensive high-efficiency development and utilization of Environmental Technology and energy-conserving and emission-cutting technology, power supply system and the material of research and development high-energy-density are imperative, the common pursuit that the research and development capacity is higher, the battery system of new generation environmental protection close friend, continuable becomes the scientist of countries in the world.
Metal-air cell, as lithium-air battery, zinc-air cell, owing to having very high specific energy, and also safe, free of contamination, in recent years, cause more and more researchers' concern.Discharge and recharge overvoltage because metal-air cell exists, make battery have very large energy loss at charge and discharge process, greatly reduce the battery Rechargeability, thereby reduced charge and discharge cycles efficient and the cycle performance of battery.Therefore how to accelerate the oxygen reduction reaction of air electrode charge and discharge process, improve the key that charge and discharge cycles efficient and cycle performance become research.Present many employing manganese dioxide etc. are as the catalyst of air electrode, but its current density is lower, in order to improve its current density, have from improving technique or preparation method and set about, as use the solidifying limb of colloidal sol to prepare manganese dioxide-catalyst, this method has improved the catalytic performance of manganese dioxide a little, but its its preparation process is complicated, and preparation cost is higher; Another kind method is to add auxiliary substance in manganese dioxide, as Co, Li or rare earth element, what its current density was more traditional slightly promotes with the current density of manganese dioxide as the air electrode of catalyst, but still on the low side, and the catalyst price is more expensive, makes the battery cost higher.Therefore, need the new and effective air electrode of research and development, to improve the performance of metal-air cell.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of air electrode in order to overcome existing use noble metal catalyst with defectives such as use are on the low side with the air electrode current density of the metal-air cell of the main catalyst of manganese dioxide, price is higher, production cost is low, and the catalyst preparation that this air electrode uses is simple, price is lower and use this catalyst to make the current density of air electrode be improved preferably.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of novel air electrode for metal-air cell, compressing by Catalytic Layer, diffusion layer and current collection layer, the catalyst in Catalytic Layer is TiO
2/ graphen catalyst.
Described TiO
2/ graphen catalyst is made by following methods: be rare nitric acid treatment Graphene of 10% with volumetric concentration, filter, distilled water repeatedly washs, and oven dry is ground, look over so as to check, with mass ratio be the TiCl of 1～10 times of Graphene
4Solution is 0 ℃～10 ℃ reactions that are hydrolyzed, and product is calcined under 300 ℃～900 ℃, grinds to get TiO after being cooled to room temperature
2/ graphen catalyst.
Described Catalytic Layer comprises that percentage by weight is 5～50% catalyst, 30～80% material with carbon element, 0～10% polyethylene glycol, 5～10% absolute ethyl alcohol and 5～25% polytetrafluoroethylene; Described diffusion layer comprises that percentage by weight is 20～60% material with carbon element, 5～30% pore creating material, 5～10% absolute ethyl alcohol and 10～60% polytetrafluoroethylene.
Described material with carbon element is that weight ratio is active carbon and the acetylene black of 5:l.
Described pore creating material is polyethylene glycol.
Described Catalytic Layer, diffusion layer and current collection layer are compressing under 15～35Mpa.
Described current collection layer is conducting copper mesh.
The preparation of described Graphene: 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.
Compared with prior art, beneficial effect of the present invention is as follows:
L, TiO of the present invention
2/ graphen catalyst is the TiCl by cheapness
4One step steam hydrolysis reacts the grained catalyst for preparing and get, with general preparation nano-TiO
2That method is different is TiCl
4Realized TiO in the time of by the graphene uniform adsorption of hydrolyzation
2Uniform load distribute, removed traditional first preparation TiO from
2The complicated processes of load again after colloidal sol or nano particle.Realized the reduction of the simple to operate and electrode production cost of catalyst preparation.
2, TiO of the present invention
2/ graphen catalyst is calcined under 300 ℃～900 ℃ and is got, and has effectively prevented TiO
2The reunion of particle has guaranteed the catalytic activity of catalyst.
3, employing TiO of the present invention
2The more traditional use of the discharge current density of the air electrode of/graphen catalyst MnO
2The discharge current density of the air electrode of catalyst is greatly improved.
4, 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.
Embodiment
In embodiment, TiCl
4Pure for analyzing, volume is respectively 6ml, 14ml, its corresponding quality is 10.36g, 24.16g, 31.07g, 37.97g by converting as can be known for 18ml, 22ml.
EXAMPLE l
Be rare nitric acid treatment 10g Graphene of 10% with volumetric concentration, filter, distilled water repeatedly washs, and 80 ℃ of oven dry are ground, and look over so as to check (400 mesh sieve) makes the Graphene after processing, is cooled to below 10 ℃; Pipette the TiCl of 0 ℃～10 ℃
4Solution 6ml slowly injects the Graphene after processing, constantly stirs, until overflow without white acid mist, hydrolysis is completed, and product is calcined under 500 ℃, grinds to get described TiO after being cooled to room temperature
2/ graphen catalyst.Get percentage by weight and be 5% above-mentioned catalyst, 60% material with carbon element (active carbon and acetylene black, weight ratio are 5:1), 8% polyethylene glycol, 7% absolute ethyl alcohol and 20% polytetrafluoroethylene mix to roll makes Catalytic Layer; Get percentage by weight and be 20% material with carbon element (active carbon and acetylene black, weight ratio is 5:1), 30% pore creating material (polyethylene glycol), 10% absolute ethyl alcohol and 40% polytetrafluoroethylene mix to roll makes diffusion layer, Catalytic Layer, conducting copper mesh and diffusion layer are compressing under 25Mpa, make TiO
2/ graphen catalyst.
Embodiment 2
Be rare nitric acid treatment 8g Graphene of 10% with volumetric concentration, filter, distilled water repeatedly washs, and 80 ℃ of oven dry are ground, and look over so as to check (400 mesh sieve) makes the Graphene after processing, is cooled to below 10 ℃; Pipette the TiCl of 0 ℃～10 ℃
4Solution 14ml slowly injects the Graphene after processing, constantly stirs, until overflow without white acid mist, hydrolysis is completed, and product is calcined under 800 ℃, grinds to get described TiO after being cooled to room temperature
2/ graphen catalyst.Get percentage by weight and be 50% above-mentioned catalyst, 30% material with carbon element (active carbon and acetylene black, weight ratio are 5:1), 5% polyethylene glycol, 5% absolute ethyl alcohol and 10% polytetrafluoroethylene mix to roll makes Catalytic Layer; Get percentage by weight and be 50% material with carbon element (active carbon and acetylene black, weight ratio is 5:1), 20% pore creating material (polyethylene glycol), 10% absolute ethyl alcohol and 20% polytetrafluoroethylene mix to roll makes diffusion layer, Catalytic Layer, collector (conducting copper mesh) and diffusion layer are compressing under 15Mpa, make TiO
2/ graphen catalyst.
Embodiment 3
Be rare nitric acid treatment 12g Graphene of 10% with volumetric concentration, filter, distilled water repeatedly washs, and 80 ℃ of oven dry are ground, and look over so as to check (400 mesh sieve) makes the Graphene after processing, is cooled to below 10 ℃; Pipette the TiCl of 0 ℃～10 ℃
4Solution 18ml slowly injects the Graphene after processing, constantly stirs, until overflow without white acid mist, hydrolysis is completed, and product is calcined under 700 ℃, grinds to get described TiO after being cooled to room temperature
2/ graphen catalyst.Get percentage by weight and be 30% above-mentioned catalyst, 50% material with carbon element (active carbon and acetylene black, weight ratio are 5:1), 2% polyethylene glycol, 5% absolute ethyl alcohol and 13% polytetrafluoroethylene mix to roll makes Catalytic Layer; Get percentage by weight and be 40% material with carbon element (active carbon and acetylene black, weight ratio is 5:1), 20% pore creating material (polyethylene glycol), 5% absolute ethyl alcohol and 35% polytetrafluoroethylene mix to roll makes diffusion layer, Catalytic Layer, collector (conducting copper mesh) and diffusion layer are compressing under 20Mpa, make TiO
2/ graphen catalyst.
Embodiment 4
Be rare nitric acid treatment 12g Graphene of 10% with volumetric concentration, filter, distilled water repeatedly washs, and 80 ℃ of oven dry are ground, and look over so as to check (400 mesh sieve) makes the Graphene after processing, is cooled to below 10 ℃; Pipette the TiCl of 0 ℃～10 ℃
4Solution 22ml slowly injects the Graphene after processing, constantly stirs, until overflow without white acid mist, hydrolysis is completed, and product is calcined under 900 ℃, grinds to get described TiO after being cooled to room temperature
2/ graphen catalyst.Get percentage by weight and be 20% above-mentioned catalyst, 40% material with carbon element (active carbon and acetylene black, weight ratio are 5:1), 10% polyethylene glycol, 10% absolute ethyl alcohol and 20% polytetrafluoroethylene mix to roll makes Catalytic Layer; Get percentage by weight and be 35% material with carbon element (active carbon and acetylene black, weight ratio is 5:1), 25% pore creating material (polyethylene glycol), 8% absolute ethyl alcohol and 32% polytetrafluoroethylene mix to roll makes diffusion layer, Catalytic Layer, collector (conducting copper mesh) and diffusion layer are compressing under 35Mpa, make TiO
2/ graphen catalyst.
Claims (8)
1. a novel air electrode that is used for metal-air cell, compressing by Catalytic Layer, diffusion layer and current collection layer, it is characterized in that, the catalyst in described Catalytic Layer is TiO
2/ graphen catalyst.
2. as a kind of novel air electrode for metal-air cell as described in claim l, it is characterized in that described TiO
2/ graphen catalyst is made by following methods: be rare nitric acid treatment Graphene of 10% with volumetric concentration, filter, distilled water repeatedly washs, and oven dry is ground, look over so as to check, with mass ratio be the TiCl of 1～10 times of Graphene
4Solution is 0 ℃～10 ℃ reactions that are hydrolyzed, and product is calcined under 300 ℃～900 ℃, grinds to get TiO after being cooled to room temperature
2/ graphen catalyst.
3. as a kind of novel air electrode for metal-air cell as described in claim l or 2, it is characterized in that, described Catalytic Layer comprises that percentage by weight is 5～50% catalyst, 30～80% material with carbon element, 0～10% polyethylene glycol, 5～10% absolute ethyl alcohol and 5～25% polytetrafluoroethylene; Described diffusion layer comprises that percentage by weight is 20～60% material with carbon element, 5～30% pore creating material, 5～10% absolute ethyl alcohol and 10～60% polytetrafluoroethylene.
4. a kind of novel air electrode for metal-air cell as claimed in claim 3, is characterized in that, described material with carbon element is that weight ratio is active carbon and the acetylene black of 5:l.
5. a kind of novel air electrode for metal-air cell as claimed in claim 4, is characterized in that, described pore creating material is polyethylene glycol.
6. a kind of novel air electrode for metal-air cell as claimed in claim 3, is characterized in that, described Catalytic Layer, diffusion layer and current collection layer are compressing under 15～35Mpa.
7. a kind of novel air electrode for metal-air cell as claimed in claim 6, is characterized in that, described current collection layer is conducting copper mesh.
8. a kind of novel air electrode for metal-air cell as claimed in claim 1, is characterized in that the preparation of described Graphene: 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.
Priority Applications (1)
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| CN201310066291XA CN103151532A (en) | 2013-03-01 | 2013-03-01 | Novel air electrode for metal-air battery |
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| CN201310066291XA CN103151532A (en) | 2013-03-01 | 2013-03-01 | Novel air electrode for metal-air battery |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682376A (en) * | 2013-12-20 | 2014-03-26 | 清华大学 | Method for preparing air electrode, air electrode and battery comprising air electrode |
| CN104701555A (en) * | 2015-03-17 | 2015-06-10 | 济宁利特纳米技术有限责任公司 | Air electrode of zinc-air battery based on graphene and preparation method thereof |
| CN105186007A (en) * | 2015-06-26 | 2015-12-23 | 浙江大学 | Nanostructure Ti/TiO2 composite electrode, preparation method and application thereof |
| CN106887580A (en) * | 2017-04-27 | 2017-06-23 | 中南大学 | A kind of lithium ion battery negative material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142537A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene/MoS2 compound nano material lithium ion battery electrode and preparation method thereof |
| CN102255086A (en) * | 2011-04-02 | 2011-11-23 | 中国科学院海洋研究所 | Graphene-based composite air electrode catalyst and preparation method thereof |
| CN102324527A (en) * | 2011-08-31 | 2012-01-18 | 上海尧豫实业有限公司 | Air electrode of zinc-air battery |
-
2013
- 2013-03-01 CN CN201310066291XA patent/CN103151532A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102142537A (en) * | 2011-02-25 | 2011-08-03 | 浙江大学 | Graphene/MoS2 compound nano material lithium ion battery electrode and preparation method thereof |
| CN102255086A (en) * | 2011-04-02 | 2011-11-23 | 中国科学院海洋研究所 | Graphene-based composite air electrode catalyst and preparation method thereof |
| CN102324527A (en) * | 2011-08-31 | 2012-01-18 | 上海尧豫实业有限公司 | Air electrode of zinc-air battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682376A (en) * | 2013-12-20 | 2014-03-26 | 清华大学 | Method for preparing air electrode, air electrode and battery comprising air electrode |
| CN104701555A (en) * | 2015-03-17 | 2015-06-10 | 济宁利特纳米技术有限责任公司 | Air electrode of zinc-air battery based on graphene and preparation method thereof |
| CN104701555B (en) * | 2015-03-17 | 2019-09-03 | 济宁利特纳米技术有限责任公司 | A kind of air electrode of zinc-air cell and preparation method thereof based on graphene |
| CN105186007A (en) * | 2015-06-26 | 2015-12-23 | 浙江大学 | Nanostructure Ti/TiO2 composite electrode, preparation method and application thereof |
| CN105186007B (en) * | 2015-06-26 | 2018-06-01 | 浙江大学 | The Ti/TiO of nanostructured2Combination electrode and its preparation method and application |
| CN106887580A (en) * | 2017-04-27 | 2017-06-23 | 中南大学 | A kind of lithium ion battery negative material and preparation method thereof |
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Application publication date: 20130612 |