CN103219526A - Cellular morphology lithium-air battery anode with hierarchical porous structure, and preparation method thereof - Google Patents
Cellular morphology lithium-air battery anode with hierarchical porous structure, and preparation method thereof Download PDFInfo
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- CN103219526A CN103219526A CN2013101128811A CN201310112881A CN103219526A CN 103219526 A CN103219526 A CN 103219526A CN 2013101128811 A CN2013101128811 A CN 2013101128811A CN 201310112881 A CN201310112881 A CN 201310112881A CN 103219526 A CN103219526 A CN 103219526A
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Abstract
The invention belongs to the technical field of lithium-air batteries, and particularly relates to a cellular morphology lithium-air battery anode with a hierarchical porous structure, and a preparation method of the lithium-air battery anode. The preparation method takes a silica sphere as a template and glucose as carbon source, and cellular carbon material with the hierarchical porous structure can be synthesized under the nitrogen atmosphere; and the cellular carbon material is taken as a carrier, diaphragm Celgard 3500 is taken as a substrate, polytetrafluoroethylene is taken as an adhesive, and the lithium-air battery anode can be prepared in a coating way. The method is simple in technology and good in reproducibility, and the prepared carbon material is even in structural distribution. After the lithium-air battery anode is applied, the lithium oxide formed in the discharge process can be contained by macropores, and the pores are not blocked, so that high air diffusivity can be well maintained, and the battery has better rate capability; and the nanopores are beneficial for forming a gas-liquid-solid three-phase reaction interface.
Description
Technical field
The invention belongs to the lithium-air battery technical field, be specifically related to a kind of lithium-air battery positive pole and preparation method thereof with multi-stage artery structure honeycomb pattern.
Background technology
Lithium-air battery (claiming lithium-oxygen battery again), the porous carbon that adopts high-specific surface area is as positive pole, and lithium metal is as negative pole.1996, K. M. Abraham reported first be electrolytical lithium/air cell with gelatin polymer (PAN – PVDF), this battery operated voltage is between 2.0-2.8 V, with the phthalocyanine cobalt as air electrode catalyst, has good coulombic efficiency [K. M. Abraham and Z. Jiang, J. Electrochem. Soc., 143(1996) 1].In the lithium-air battery discharge process, can directly from air, extract O
2As positive active material, reduce the gross mass of battery greatly, its specific discharge capacity is up to 3862 mAh/g, and theoretical specific capacity is 11140 Wh/kg, is common more than 10 times of lithium ion battery.
The development of lithium air is subjected to the restriction of all many-sides, wherein is exactly the influence of anodal material with carbon element but at present.Oxygen reduction reaction and the main place of holding discharging product as taking place in air electrode, and the equal profound influence of its preparation method and physical characteristic specific discharge capacity, high rate performance and the cycle performance of battery.Good electrochemical all has certain requirement to material with carbon element specific area, porosity, pore-size distribution and carbon load capacity and thickness of electrode, wherein with to pore-size distribution influence for very.In battery discharge procedure, the lithium oxide deposits at electrode surface, stops up aperture and influences medium transmission; On the contrary, mesoporous and large pore material can hold the discharging product of some and not influence the diffusion of oxygen, makes it stop discharge [C. Tran along with quantity is tending towards saturated, X.Q. Yang, D.Y. Qu, J. Power Sources, 195 (2010) 2057].Putting before this, synthetic and modify the material with carbon element of mesopore/macropore or the material with carbon element of multi-stage artery structure becomes new research direction.Ji-Guang Zhang has been combined into the three-dimensional poroid Graphene of micron-scale and nano-scale coexistence for a short time.In the hydrogen reduction process, the hole of micron-scale helps the transmission and the diffusion of oxygen, and the hole of nano-scale both can be used as reaction site, help the formation of gas-solid liquid three phase boundary again, its discharge capacity can be up to 15000 mAh/g[J. Xiao and J.G. Zhang, Nano Lett., 11 (2011) 5071].Xinbo Zhang group adopts " in situ sol-gel " method, is carbon source and skeleton with the graphene oxide, and phenolic resins has synthesized the carbon-coating structure with three-dimensional multi-stage artery structure as carbon source.Wherein, aperture and mesoporous existence reduce the ion transport path, impedance [Z.L. Wang, D. Xu, the J.J. Xu of pole piece inside have been reduced effectively, L.L. Zhang and X.B. Zhang, Adv. Funct. Mater., 22 (2012) 3699].
Summary of the invention
The lithium-air battery positive electrode and preparation method thereof that the purpose of this invention is to provide the honeycomb pattern of a kind of function admirable, the simple tool multi-stage artery structure of preparation.
The lithium-air battery positive pole of the honeycomb pattern of the tool multi-stage artery structure that the present invention proposes, be as carrier with honeycomb material with carbon element with multi-stage artery structure, barrier film (Celgard 3500) is as substrate, and polytetrafluoroethylene (PVDF) prepares by the mode that is coated with as binding agent.
The preparation method of the lithium-air battery positive pole of the honeycomb pattern of the tool multi-stage artery structure that the present invention proposes at first, is a template with the silica spheres, and glucose is the synthetic honeycomb material with carbon element with multi-stage artery structure of carbon source; Then, the honeycomb material with carbon element prepares the lithium-air battery positive pole as carrier.Concrete steps are:
A, 8-10 ml tetraethoxysilane (TEOS) joined contain 25-35 ml ethanol, in the mixed solution of 8-10 ml deionized water and 1.5-2.5 ml 25-28% ammoniacal liquor, keep 1 h down at 30-35 ℃, oven dry is spent the night under 85-95 ℃, obtains the silicon dioxide ball template of internal diameter 350-450 nm;
B, with 0.8-1.2 g silica template, 0.5-0.8 g glucose joins in the 50-80 ml deionized water, is stirred to all solvent evaporations under 70-75 ℃ of water-bath; Little yellow solid of gained rises to 850 ℃ and keep 3 h with 5 ℃/min in nitrogen atmosphere after grinding; At last, remove silica template, obtain the honeycomb material with carbon element of tool multi-stage artery structure with the immersion of 10-20% HF solution;
C, the honeycomb material with carbon element of gained is made air electrode, be about to honeycomb material with carbon element and PVDF (2-2.5) in proportion: 1 weight is mixed, with N-methyl pyrrolidone (NMP) is that solvent is sized mixing, evenly coat barrier film (Celgard 3500), dry the back in the air and in 70-80 ℃ vacuum drying oven, keep 12-15 h; Control carrying capacity (being the summation of honeycomb material with carbon element and PVDF quality) is 1-2 mg/cm
2
The inventive method, technology is simple, favorable reproducibility, the honeycomb material with carbon element structure distribution of preparation is even.Compared with the prior art, beneficial effect of the present invention is embodied in:
Macropore in the multi-stage artery structure can hold the insoluble product that produces in the discharge process and unlikely obstruction gas passage helps to reduce overpotential, obtains stable interface impedance and bigger high rate performance; The aperture of nano-scale helps forming gas-liquid-solid three-phase reaction interface, obtains specific discharge capacity preferably.
Description of drawings
Fig. 1 is the stereoscan photograph of product.Wherein, a, b are the sem photograph of HCC-400, and c, d are the sem photograph of HCC-100.
Fig. 2 is that the chemical property of product HCC-400 and conventional material with carbon element Super P compares.Wherein, a is 0.05 mA cm
-2Discharging current under chemical property, b is 0.2 mA cm
-2Discharging current under chemical property.
Fig. 3 is that product HCC-400 and conventional material with carbon element Super P are at 0.2 mA cm
-2Electrochemistry cycle graph under the discharging current.
Fig. 4 is product HCC-400 and the first discharge curve of HCC-100 under different discharging currents.Wherein, a is 0.05mA cm
-2Current density, b is 0.2mA cm
-2Current density, c is 0.5mA cm
-2Current density.
Fig. 5 is that the control discharge capacity is at 1000mAh g
-1The time, the cut-ff voltage of product HCC-400 and HCC-100.
Embodiment
Below by embodiment, the present invention program is further described in detail.
Embodiment 1
1,10 ml tetraethoxysilanes (TEOS) joined contain 30 ml ethanol, in the mixed solution of 10 ml deionized waters and 2 ml 25-28% ammoniacal liquor, keep 1 h down at 30 ℃, in 90 ℃ down oven dry spend the night and obtain the silica template of aperture 400 nm.
2, with 1.0 g silica templates, 0.5 g glucose joins in the 50 ml deionized waters, is stirred to all solvent evaporations under 70 ℃ of water-baths; Little yellow solid of gained rises to 850 ℃ and keep 3 h with 5 ℃/min in nitrogen atmosphere after grinding; At last, remove silica template, obtain the honeycomb material with carbon element of tool multi-stage artery structure with the immersion of 10% HF solution.
3, the honeycomb material with carbon element of gained is made air electrode, be about to honeycomb material with carbon element and PVDF in proportion the weight of 2:1 to mix with N-methyl pyrrolidone (NMP) be that solvent is sized mixing, be uniformly coated on barrier film, dry the back in the air and in 80 ℃ vacuum drying oven, keep 12 h.
Presentation of results:
(a) accompanying drawing 2 explanation adopts multistage pore canal honeycomb material with carbon elements as the air electrode of carrier and the Super P air electrode as carrier, with regard to chemical property, no matter the former is on specific discharge capacity and operating platform voltage, all far above the latter, effectively reduce the overpotential in the charge and discharge process, have better invertibity and high rate performance.
(b) as can be seen, by accompanying drawing 3 adopt multistage pore canal honeycomb material with carbon element as the air electrode of carrier because itself its specific structure, at 0.2 mA cm
-2Discharging current under, can stable circulation 12 circles, and adopt the battery of Super P as the air electrode of carrier, under the same test condition, specific discharge capacity is sharply decayed.
Comparative example 1-1
With Super P and PVDF in proportion the weight of 2:1 to mix with N-methyl pyrrolidone (NMP) be that solvent is sized mixing, be uniformly coated on barrier film, dry the back in the air and in 80 ℃ vacuum drying oven, keep 12 h.
Comparative example 1-2
Except that the silica template aperture of being adopted is 100 nm, other steps are identical with embodiment 1.The silicon dioxide ball template synthesis step of internal diameter 100 nm is as follows: tetraethoxysilane ethanolic solution 200 ml of preparation 6%, add the deionized water of 8 ml and the ammoniacal liquor of 8 ml 25-28%, and stir 24 h under the room temperature, can obtain in 70 ℃ of following dryings.
Presentation of results:
(a) accompanying drawing 4 explanations, under the same test condition, the honeycomb carbon of aperture 100 nm has bigger specific area, thereby shows bigger specific discharge capacity and better high rate performance.
(b) as can be seen, controlling specific discharge capacity at 1000 mAh g by accompanying drawing 3
-1, the honeycomb carbon of aperture 100 nm has better cycle ability, still can keep the cut-ff voltage of 2.42 V when the 9th circle.
In sum, the present invention is by adopting silica spheres as template, and glucose has synthesized a kind of honeycomb material with carbon element with multi-stage artery structure as carbon source.It is introduced the lithium-air battery air electrode as carrier, in discharge process, both helped the deposition of discharging product and do not influenced the diffusion of gas in electrode interior, and the aperture of nano-scale is especially effectively in forming three-phase reaction interface, thereby improved discharge capacity, also improved cycle performance and high rate performance.This design and preparation technology have novelty very much.Be hopeful and use in the lithium-air battery under field conditions (factors).
Claims (2)
1. have an air electrode of lithium-air battery of honeycomb pattern of multi-stage artery structure, it is characterized in that it being as carrier with honeycomb material with carbon element with multi-stage artery structure, barrier film Celgard 3500 is as substrate, and polytetrafluoroethylene prepares by the mode that is coated with as binding agent.
2. preparation method as lithium-air battery air electrode as described in the claim 1 is characterized in that concrete steps are as follows:
A, 8-10 ml tetraethoxysilane joined contain 25-35 ml ethanol, in the mixed solution of 8-10 ml deionized water and 1.5-2.5 ml 25-28% ammoniacal liquor, keep 1 h down at 30-35 ℃, oven dry is spent the night under 85-95 ℃, obtains the silicon dioxide ball template of internal diameter 350-450 nm;
B, with 0.8-1.2 g silica template, 0.5-0.8 g glucose joins in the 50-80 ml deionized water, is stirred to all solvent evaporations under 70-75 ℃ of water-bath; Little yellow solid of gained rises to 850 ℃ and keep 3 h with 5 ℃/min in nitrogen atmosphere after grinding; At last, remove silica template, obtain the honeycomb material with carbon element of tool multi-stage artery structure with the immersion of 10-20% HF solution;
C, the honeycomb material with carbon element of gained is made air electrode, being about to the honeycomb material with carbon element mixes by the part by weight of 2-2.5:1 with PVDF, with the N-methyl pyrrolidone is that solvent is sized mixing, evenly coat on the barrier film Celgard 3500, dry the back in the air and in 70-80 ℃ vacuum drying oven, keep 12-15 h; The control carrying capacity is 1-2 mg/cm
2
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103904340A (en) * | 2014-03-31 | 2014-07-02 | 华南师范大学 | Porous carbon with uniform nano aperture as well as preparation method thereof and application |
| CN105817202A (en) * | 2016-05-26 | 2016-08-03 | 江苏大学 | Preparation method and application of three-dimensional lignin-based hierarchical pore activated carbon material |
| CN106129425A (en) * | 2016-09-21 | 2016-11-16 | 许昌学院 | A kind of porous carbon electrode material and its preparation method and application |
| CN111017902A (en) * | 2019-12-17 | 2020-04-17 | 陕西师范大学 | Preparation method of three-dimensional continuous porous carbon material |
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| CN102208653A (en) * | 2010-08-31 | 2011-10-05 | 中国科学院上海硅酸盐研究所 | Air electrode of lithium air battery and preparation method thereof |
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| US6110621A (en) * | 1998-11-24 | 2000-08-29 | The University Of Chicago | Carbons for lithium batteries prepared using sepiolite as an inorganic template |
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| CN103904340A (en) * | 2014-03-31 | 2014-07-02 | 华南师范大学 | Porous carbon with uniform nano aperture as well as preparation method thereof and application |
| CN105817202A (en) * | 2016-05-26 | 2016-08-03 | 江苏大学 | Preparation method and application of three-dimensional lignin-based hierarchical pore activated carbon material |
| CN106129425A (en) * | 2016-09-21 | 2016-11-16 | 许昌学院 | A kind of porous carbon electrode material and its preparation method and application |
| CN111017902A (en) * | 2019-12-17 | 2020-04-17 | 陕西师范大学 | Preparation method of three-dimensional continuous porous carbon material |
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Application publication date: 20130724 |