CN102569822A - Anti-blocking air electrode for Li-air battery - Google Patents

Anti-blocking air electrode for Li-air battery Download PDF

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Publication number
CN102569822A
CN102569822A CN2010105755476A CN201010575547A CN102569822A CN 102569822 A CN102569822 A CN 102569822A CN 2010105755476 A CN2010105755476 A CN 2010105755476A CN 201010575547 A CN201010575547 A CN 201010575547A CN 102569822 A CN102569822 A CN 102569822A
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air
electrode
air electrode
layer
lithium
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CN2010105755476A
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Chinese (zh)
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丁飞
刘兴江
桑林
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中国电子科技集团公司第十八研究所
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Priority to CN2010105755476A priority Critical patent/CN102569822A/en
Publication of CN102569822A publication Critical patent/CN102569822A/en

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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/50Fuel cells

Abstract

The invention relates to an anti-blocking air electrode for a Li-air battery, comprising a current collector and an air reaction layer, wherein an air transport layer is compounded on the air reaction layer, and the air transport layer is a single layer or more than overlapped two layers of insulating porous thin-film materials. According to the invention, by using the air transport layer made from insulating porous thin-film materials, air can be transported in three dimensional direction, air can smoothly enter the side which belongs to the air electrode and is positioned adjacently to the lithium electrode under the condition of increasing the thickness of the air electrode, thus the failure of the air electrode caused by the blocking of the side towards to the air of the air electrode is avoided, the air electrode has high specific energy and high usage life, and simultaneously the performance of the air electrode in heavy current is raised, and finally the capacity and current density of the Li-air battery are raised.

Description

锂空气电池用防阻塞空气电极 Lithium air battery antiblocking air electrode

技术领域 FIELD

[0001] 本发明属于锂空气电池技术领域,特别是涉及一种锂空气电池用防阻塞空气电极。 [0001] The present invention belongs to the field of lithium-air battery technology, particularly to a lithium-air battery with an antiblocking air electrode.

背景技术 Background technique

[0002] 锂空气电池是以金属锂作为负极,空气电极为正极的高比能量电池,其预计可实现的比能量为1000Wh/kg以上,是新一代高能电池。 [0002] The lithium air battery is a lithium metal as a negative electrode, an air electrode as a positive electrode of high specific energy battery which is expected to achieve specific energy is at least 1000Wh / kg, a new generation of high-energy battery.

[0003] 目前,对锂空气电池的研究按照所采用电解液的不同可以分为水体系锂空气电池和有机体系(即非水体系)锂空气电池。 [0003] Currently, research on a lithium air battery electrolytic solution can be divided in different aqueous lithium air battery systems and organic systems (i.e., non-aqueous systems) lithium air battery is employed. 其中有机体系锂空气电池,由于制备简单、安全性更高,获得更广泛的研究。 Wherein the organic lithium air battery system, since the preparation is simple, more secure, more widely studied. 在空气电极的制备中,为了使空气电池具有较高的容量、较高的工作电流密度,就要有大容量的空气电极,则要加大空气电极的厚度。 In the preparation of the air electrode, in order to make the air battery having a higher capacity, higher operating current density, the air electrode must have a large capacity, it will have to increase the thickness of the air electrode.

[0004] 但是在有机体系锂空气电池的研究中发现,随着空气电极厚度的增加,空气电极的比能量以及循环性能出现了逐渐下降的状况。 [0004] However, the lithium air battery system of organic found, with the increase of the thickness of the air electrode, the specific energy and cycle performance of the air electrode occurs a gradual decline in health. 这主要是因为在较厚空气电极中反应产物优先在空气一侧发生堆积,同时发现空气电极电流密度的提高会加剧反应产物在空气电极空气侧的阻塞,导致空气电极面向负极的一侧放电容量不能充分发挥,使得空气电极的性能下降或提前失效而影响空气电极的比能量和循环寿命。 This is mainly because the reaction product occurs preferentially accumulate in thick air electrode side in the air while blocking the air electrode current density was found to improve the reaction product will intensify the air side of the air electrode, resulting in the discharge capacity of the negative side facing the air electrode not be sufficiently exhibited, so that the performance of the air electrode is lowered or failure affects the specific energy of the air electrode and the cycle life in advance.

发明内容 SUMMARY

[0005] 本发明的目的是克服现有技术的不足之处,提供一种锂空气电池用防阻塞空气电极,该空气电极具有空气电极厚度和容量大时无阻塞,制成的锂空气电池容量和工作电流密度高,并且空气电极的比能量和循环性能高的特点。 [0005] The object of the present invention is to overcome the shortcomings of the prior art, there is provided a lithium-air battery electrode antiblocking, blocking the air electrode having an air electrode thickness and large capacity, made of a lithium air battery capacity and a high operating current density, and high specific energy and cycle performance characteristics of the air electrode.

[0006] 本发明锂空气电池用防阻塞空气电极采用如下技术方案: [0006] The lithium-air battery of the present invention employs the following technical solution with antiblocking air electrode:

[0007] 锂空气电池用防阻塞空气电极,包括集流体、空气反应层,其特征在于:所述空气反应层上复合有空气传输层,所述空气传输层为单层或两层以上重叠的绝缘性多孔薄膜材料。 [0007] The lithium-air battery with an anti blocking the air electrode comprising a current collector, an air reaction layer, wherein: the upper air layers of the composite reaction layer of air transport, the air-transport layer is a single layer or two or more layers overlapped The porous insulating film material.

[0008] 而且,所述绝缘性多孔薄膜材料为非编织聚丙烯毛毡或玻璃纤维膜。 [0008] Further, the insulating material is non-woven polypropylene porous film or felt of glass fiber membranes.

[0009] 而且,所述绝缘性多孔薄膜材料的单层厚度为5 μ m-500 μ m,空气反应层的厚度为10 μ m-2000 μ m0 [0009] Further, the insulating layer thickness of the porous film material is 5 μ m-500 μ m, thickness of the air layer of the reaction 10 μ m-2000 μ m0

[0010] 而且,所述空气电极为卷绕状、叠层状或折片状结构。 [0010] Further, the air electrode is a coil-shaped, sheet-like structure or a folded stack.

[0011] 本发明具有的优点和积极效果: [0011] The present invention has advantages and positive effects:

[0012] 本发明空气电极由于采用了多孔薄膜绝缘材料的空气传输层,空气在三维方向上均可以传输,在加大空气电极厚度情况下,空气可以顺利进入到空气电极与锂电极贴近的一侧,避免了因空气电极朝向空气一侧的阻塞导致空气电极的失效,空气电极在具有高比能量和高使用寿命的同时,又提高了空气电极在大电流工作下的性能,最终提高锂空气电池容量和电流密度。 [0012] an air electrode of the present invention adopts an air-transport layer porous film of the insulating material, air can be transmitted in three dimensions, in the case of increasing the thickness of the air electrode, air may smoothly into the air electrode and the lithium electrode proximate to a side, to avoid blocking the air due to the air electrode side toward lead to failure of the air electrode, air electrode, while having a high specific energy and high durability, but also improves the performance of the air electrode at a large current, and ultimately improved lithium-air battery capacity and current densities.

3附图说明 BRIEF DESCRIPTION 3

[0013] 图1是本发明锂空气电池用防阻塞空气电极断面结构示意图; [0013] FIG. 1 is a lithium-air battery of the present invention, a clogging preventing a schematic cross-sectional structure of the air electrode;

[0014] 图2是图1的电极卷绕状断面结构示意图; [0014] FIG. 2 is a schematic sectional structure of a coil-shaped electrode of Figure 1;

[0015] 图3是图1的电极叠片状断面结构示意图; [0015] FIG. 3 is a sectional schematic view of a sheet-like structure of the electrode stack of FIG 1;

[0016] 图4是图1的电极折片状断面结构示意图; [0016] FIG. 4 is a schematic cross-sectional structure of the electrode off the sheet of Figure 1;

[0017] 图5是本发明空气电极制备的锂空气电池的比能量结果图。 [0017] FIG. 5 is a specific energy of lithium-air battery results in FIG air electrode of the present invention is prepared.

[0018] 其中,1-集流体,2-空气反应层,3-空气传输层。 [0018] wherein the current collector 1-, 2- reaction air layer, 3 an air transport layer.

具体实施方式 Detailed ways

[0019] 下面结合附图并通过具体实施例对本发明作进一步详述,以下实施例只是描述性的,不是限定性的,不能以此限定本发明的保护范围。 [0019] conjunction with the accompanying drawings and the following specific embodiments of the present invention will be further described in detail, for example, the following embodiments merely descriptive, not limiting, in order not to limit the scope of the present invention.

[0020] 本发明锂空气电池用防阻塞空气电极,包括集流体、厚度为10μπι-2000μπι的空气反应层,空气反应层上复合有空气传输层,所述空气传输层为单层或两层以上重叠的绝缘性多孔薄膜材料,绝缘性多孔薄膜材料采用单层厚度为5 μ m-500 μ m的非编织聚丙烯毛毡或玻璃纤维膜,这些多孔薄膜材料在三维方向上均具有良好的空气传输性能,可以使空气在三维方向上均可以传输,保证空气自由的进入并传输到空气电极朝向锂电极的一侧, 以增加空气扩散层的厚度,提高空气在空气传输层中的传输速度。 [0020] The lithium-air battery of the present invention with an anti blocking the air electrode includes a current collector, the thickness of the air layer 10μπι-2000μπι of the reaction, the reaction layer of the composite air air-transport layer, the transport layer is a single layer of air or more layers overlapping a porous insulating film material, the insulating material is a single-layer porous film having a thickness of 5 μ m-500 μ m of a polypropylene felt or non-woven glass fiber membrane, the porous film material in three dimensions have good air delivery performance, the air can be transmitted in three dimensions, ensure access to free air side of the air electrode and transmitted to the lithium electrode facing to increase the thickness of the air diffusion layer, increasing the air transmission rate in air transport layer. 但如果空气扩散层具有导电性,电极反应则有可能在扩散层中发生,而反应产物将逐渐阻塞空气扩散层,导致空气扩散层性能下降,因此选用绝缘性多孔薄膜材料。 But if the air diffusion layer having a conductivity, the electrode reactions may occur in the diffusion layer, and the reaction product was gradually blocking the air diffusion layer, resulting in an air diffusion layer performance degradation, and therefore a porous insulating film material chosen. 制成的空气电极可以为卷绕状、叠层状或折片状结构。 The air electrode may be made of a coil-shaped, sheet-like structure or a folded stack.

[0021 ] 实施例1 :参照附图1-图4。 [0021] Example 1: Referring to the drawings 1 through 4.

[0022] 锂空气电池用防阻塞空气电极的制作 [0022] A lithium-air battery antiblocking air electrode

[0023] 将厚度为20um的非编织聚丙烯毡作为空气传输层3 ;将30 % -90 %人造石墨、5% -50%聚四氟乙烯乳液为胶粘剂、0% -50% 二氧化锰催化剂混合后,在加热至400C -80°C的辊压机上反复辊压至厚度为0. lmm-3mm的均勻片层,制备出空气反应层2 ;以孔径10目-100目的铝网、钛网或铁网为集流体1,自下至上依次将集流体、空气反应层和空气传输层放置在一起,用热压机,IO-IOOOPa热压成一体,制备出图1所示锂空气电池用防阻塞空气电极。 [0023] The thickness of 20um polypropylene nonwoven as an air felt transporting layer 3; 30% -90% of artificial graphite, 5% -50% of polytetrafluoroethylene emulsion adhesives, 0-50% manganese dioxide catalyst after mixing, the heating to 400C -80 ° C roll press repeatedly rolled to a thickness of 0. lmm-3mm uniform sheet, layer 2 is prepared by reaction of the air; an aperture 10 to -100 mesh aluminum mesh object, titanium iron mesh or net for the current collector 1, from bottom to top the collector is placed in fluid, air in the reaction layer and the transport layer together with the air, by hot pressing, IO-IOOOPa integrally thermocompression to prepare a lithium air battery 1 shown in FIG. antiblocking with the air electrode.

[0024] 根据锂空气电池的需要,可以将图1所示的空气电极,以电极的一侧为轴,将电极卷绕为图2所示的卷绕状空气电极;或者将图1所示的多片空气电极进行层叠,制成图3所示的叠片状空气电极;还可以将图1所示的空气电极以Z字形折叠方式,保持一侧有集流体留出,制成图4所示的折片状空气电极。 [0024] The lithium-air battery needs to be in the air electrode shown in FIG. 1, to the side of the electrode axis, the coil-shaped wound electrode air electrode shown in FIG. 2; FIG. 1, or the laminated multi-piece air electrode, an air electrode made of a sheet stack shown in FIG. 3; the air electrode can also shown in Figure 1 to Z-folded manner, to maintain the current collector leaving one side, FIG 4 is made flap-like air electrode shown.

[0025] 本发明制备成锂空气电池的容量测试 [0025] The present invention is prepared as a lithium air battery capacity test

[0026] 用Arbin型电池充放电设备对本发明制备成锂空气电池的容量测试,考察电池工作过程中电压和电流的变化。 [0026] The charging and discharging equipment Arbin battery of the present invention to the preparation of a lithium air battery capacity test, inspection during operation of the battery voltage and current variations. 图5是本发明空气电极制备的锂空气电池的比能量结果图。 FIG 5 is a specific energy of lithium-air battery results in FIG air electrode of the present invention is prepared. 根据图5显示的测试结果看出,采用绝缘性多孔薄膜材料的空气传输层,在空气电极厚度为Icm条件下,相对于金属锂电极单位面积的空气电池容量超过500mAh,空气电极体现出非常高的比能量。 The test results shown in Figure 5 seen, the use of an air-transport layer insulating porous film material, the thickness of the air electrode Icm conditions, with respect to more than 500mAh, reflect the air electrode lithium electrode and an air cell capacity per unit area is very high the specific energy. 说明在长期放电的过程中也没有出现由于空气电极朝向空气一侧发生阻塞所造成的电池失效现象。 Since there is no description battery toward the air side of the air electrode caused by a blockage occurs in the long discharge occurs in the spent phenomenon. 由于具备畅通的空气传输层,本发明空气电极在具有高比能量和高使用寿命的同时,还具有更加良好的电流性能,最终提高锂空气电池容量和电流密度。 Since the air flow includes a transport layer, an air electrode of the present invention have both high specific energy and high durability, but also has a more favorable current performance, and ultimately improve the lithium air battery capacity and current densities.

Claims (4)

1.锂空气电池用防阻塞空气电极,包括集流体、空气反应层,其特征在于:所述空气反应层上复合有空气传输层,所述空气传输层为单层或两层以上重叠的绝缘性多孔薄膜材料。 Lithium air battery 1. The anti-blocking the air electrode comprising a current collector, an air reaction layer, wherein: the upper air layers of the composite reaction layer of air transport, the air-transport layer is a single layer or two or more superimposed insulating porous film material.
2.根据权利要求1所述的锂空气电池用防阻塞空气电极,其特征在于:所述绝缘性多孔薄膜材料为非编织聚丙烯毛毡或玻璃纤维膜。 The lithium air battery according to claim 1 antiblocking air electrode, wherein: said insulating material is a woven polypropylene porous film or felt of glass fiber membranes.
3.根据权利要求2所述的锂空气电池用防阻塞空气电极,其特征在于:所述绝缘性多孔薄膜材料的单层厚度为5 μ m-500 μ m,空气反应层的厚度为10 μ m-2000 μ m。 The lithium air battery according to claim 2 anti-blocking the air electrode, wherein: the insulating layer thickness of the porous film material is 5 μ m-500 μ m, thickness of the air layer is 10 μ reaction m-2000 μ m.
4.根据权利要求1所述的锂空气电池用防阻塞空气电极,其特征在于:所述空气电极为卷绕状、叠层状或折片状结构。 The lithium air battery according to claim 1 antiblocking air electrode, wherein: the air electrode is a coil-shaped, sheet-like structure or a folded stack.
CN2010105755476A 2010-12-07 2010-12-07 Anti-blocking air electrode for Li-air battery CN102569822A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1031158A (en) * 1987-07-06 1989-02-15 艾尔坎国际有限公司 Air cathodes and materials therefor
CN101421865A (en) * 2006-03-10 2009-04-29 埃克塞勒特龙固体公司 Air battery and manufacturing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1031158A (en) * 1987-07-06 1989-02-15 艾尔坎国际有限公司 Air cathodes and materials therefor
CN101421865A (en) * 2006-03-10 2009-04-29 埃克塞勒特龙固体公司 Air battery and manufacturing method

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