CN103000971A - Lithium air battery and production method thereof - Google Patents

Lithium air battery and production method thereof Download PDF

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CN103000971A
CN103000971A CN2011102745301A CN201110274530A CN103000971A CN 103000971 A CN103000971 A CN 103000971A CN 2011102745301 A CN2011102745301 A CN 2011102745301A CN 201110274530 A CN201110274530 A CN 201110274530A CN 103000971 A CN103000971 A CN 103000971A
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lithium
air battery
oxygen
air
nanoparticles
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CN2011102745301A
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CN103000971B (en
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乔贞美
吴生先
张会平
李志华
任晓玲
余修涛
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北汽福田汽车股份有限公司
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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
    • Y02E60/10Energy storage
    • Y02E60/12Battery technologies with an indirect contribution to GHG emissions mitigation
    • Y02E60/128Hybrid cells composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type

Abstract

The present invention discloses a lithium air battery and a production method thereof. The lithium air battery comprises an air positive electrode, a lithium negative electrode and an organic electrolyte solution filled between the air positive electrode and the lithium negative electrode, wherein one air positive electrode side surface adjacent to the organic electrolyte solution is provided with a solid electrolyte layer. According to the lithium air battery, the one air positive electrode side surface adjacent to the organic electrolyte solution is provided with the solid electrolyte layer so as to prevent the organic electrolyte solution from evaporate toward air and inhibit moisture in the air from entering into the lithium air battery, such that the lithium air battery can stably work in an opening work environment.

Description

锂空气电池及其制作方法 Lithium air battery and manufacturing method thereof

技术领域 FIELD

[0001] 本发明涉及空气电池领域,特别涉及一种锂空气电池及制作该锂空气电池的方法。 [0001] The present invention relates to an air battery, and more particularly, to a lithium-air battery and a production method for the lithium-air battery.

背景技术 Background technique

[0002] 有机体系锂空气电池在当前诸多的电池体系中具有较高的能量密度,理论能量密度为5200Wh/kg,在实际应用中,氧气由外界环境提供,因此,排除氧气的质量后,有机系锂空气电池的能量密度达到11140Wh/kg,高出现有电池体系的1-2个数量级。 [0002] The organic lithium air battery system has a battery system in the current in many high energy density, the theoretical energy density 5200Wh / kg, in practice, oxygen is supplied by the external environment, and therefore, the quality of the exclusion of oxygen, the organic based lithium air battery energy density 11140Wh / kg, higher than the conventional cell system 1-2 orders of magnitude. 因此,目前作为超越正被广泛应用的锂离子电池的高容量二次电池而备受关注。 Therefore, it is widely used as being beyond a lithium ion secondary battery of high capacity batteries have attracted much attention.

[0003] 然而,锂空气电池的研究刚刚起步,其应用仍面临着巨大的挑战。 [0003] However, the lithium-air battery research has just started, its application still faces enormous challenges. 其中,在开放的在空气气氛下工作时,锂空气电池需要解决如何防止水汽进入电解液的问题,这是因为,有机液体电解液体系容易吸收水分而导致锂负极在空气中腐蚀。 Wherein, when operating in an open air atmosphere, lithium air batteries need to address the problem of how to prevent moisture entering the electrolytic solution, since the organic liquid electrolyte system readily absorb moisture resulting in a negative electrode of lithium corrosion in air. 另外,通常的有机液体电解质存在容易挥发的问题,从而会影响电池的容量、使用寿命及电池的安全性。 Further, there is a problem generally readily volatile organic liquid electrolytes, which will affect the safety of the battery capacity, and battery life.

发明内容 SUMMARY

[0004] 本发明旨在至少解决上述技术问题之一。 [0004] The present invention aims to solve at least one of the technical problems described above.

[0005] 为此,本发明的一个目的在于提出一种能在敞开的空气环境中稳定工作的锂空气电池。 [0005] It is therefore an object of the present invention is to propose a lithium-air cell which can stably work in an open air environment.

[0006] 本发明的另一目的在于提出一种锂空气电池的制作方法。 [0006] Another object of the present invention is to provide a method for making a lithium air battery.

[0007] 为了实现上述目的,本发明第一方面提供一种锂空气电池,包括空气正极、锂负极以及填充在所述空气电极和锂负极之间的有机电解液,其中,在所述空气电极的邻近所述有机电解液的一侧表面上设置有固体电解质层。 [0007] To achieve the above object, a first aspect of the present invention to provide a lithium air battery comprising an air cathode, a lithium negative electrode, and filled between the air electrode and the negative electrode of a lithium organic electrolyte, wherein the air electrode is provided on one surface adjacent to the organic electrolytic solution has a solid electrolyte layer.

[0008] 根据本发明第一方面实施例的锂空气电池,由于在空气正极的邻近所述有机电解液的一侧表面上设置有固体电解质层,该固体电解质层既防止有机电解液向空气中挥发也可以抑制空气中的水分进入锂空气电池内部,从而使得锂空气电池能在敞开的工作环境中稳定工作。 Examples of the lithium air battery [0008] According to a first aspect of the present invention, since the side adjacent to the upper surface of the air cathode of the organic electrolyte solution with a solid electrolyte layer, the solid electrolyte layer either to prevent the organic electrolyte solution air can be suppressed volatilization of the moisture in the air into the interior of the lithium-air batteries, lithium air battery so that the stable operation in an open work environment.

[0009] 另外,根据本发明上述实施例的锂空气电池还可以具有如下附加的技术特征: [0009] Further, the lithium air battery of the above embodiments of the present invention may also have the following additional technical features:

[0010] 根据本发明的一个实施例,所述空气正极包括金属铝箔和形成于所述金属铝箔上的氧催化剂层。 [0010] According to one embodiment of the present invention, the air cathode comprises a metal foil and oxygen formed on the catalyst layer of metal foil.

[0011] 根据本发明的一个实施例,所述氧催化剂层由载体和氧催化剂材料形成,所述氧催化剂材料选自钼纳米颗粒、金纳米颗粒、a -MnO2纳米颗粒、β -MnO2纳米颗粒、y -MnO2纳米颗粒、MoN纳米颗粒、MnN纳米颗粒、三元金属氮化物中的一种或几种材料形成。 [0011] Example, the catalyst layer is formed of an oxygen carrier and oxygen catalyst material in accordance with one embodiment of the present invention, the catalyst material is selected from molybdenum oxide nanoparticles, gold nanoparticles, a -MnO2 nanoparticles, β -MnO2 nanoparticles , y -MnO2 nanoparticles, MoN nanoparticles, nanoparticles MnN, ternary metal nitrides of one or more materials.

[0012] 根据本发明的一个实施例,所述氧催化剂层中氧催化剂材料的质量含量为为氧催化剂层总质量的5%以下。 [0012] According to an embodiment of the present invention, the oxygen mass content of the catalyst material of the catalyst layer of the oxygen is 5% of the total mass of the catalyst layer is less oxygen.

[0013] 根据本发明的一个实施例,所述固体电解质层由掺杂有过渡金属元素的氮化磷酸锂构成,所述过渡金属元素包括T1、V、Cr、Mn、Fe、Co、N1、Cu、Zr、Nb、Mo、Ru、Ag、Ta、W、Pt 及Au中的一种或多种。 [0013] According to one embodiment of the present invention, the solid electrolyte layer is doped with a transition metal nitride, lithium phosphate element constituting the transition metal element include T1, V, Cr, Mn, Fe, Co, N1, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au in one or more.

[0014] 根据本发明的一个实施例,在所述掺杂有过渡金属元素的氮化磷酸锂中,所述过渡金属兀素的含有率相对于磷原子为1-50原子%。 The content of [0014] According to an embodiment of the present invention, the doped lithium transition metal phosphate with a nitride of the transition metal element Wu phosphorus atom with respect to 1 to 50 atomic%.

[0015] 根据本发明的一个实施例,所述固体电解质层由Li2 8PO3 4具.3PTQ 2构成。 [0015] According to one embodiment of the present invention, the solid electrolyte layer is made of Li2 8PO3 4 Ju .3PTQ 2.

[0016] 根据本发明的一个实施例,所述固体电解质层的厚度为O. 1-0. 2微米。 [0016] According to one embodiment of the present invention, the thickness of the solid electrolyte layer is O. 1-0. 2 microns.

[0017] 本发明第二方面提出锂空气电池的制作方法,包括以下步骤:a)提供空气正极;b)在所述空气正极的表面上沉积固体电解质层;以及c)将沉积有所述固体电解质层的空气正极、有机电解液以及锂负极依序装配成锂空气电池,其中所述空气电极的沉积有固体电解质层一侧表面与所述有机电解液相邻。 [0017] The second aspect of the present invention provides a manufacturing method of a lithium air battery, comprising the steps of: a) providing a positive air; b) depositing a solid electrolyte layer on the surface of the air cathode; and c) the deposited solid an air cathode layer, an electrolyte, an organic electrolyte and a lithium negative electrode are sequentially assembled into a lithium-air battery, wherein said air electrode is deposited with a side surface of the solid electrolyte layer adjacent to the organic electrolytic solution.

[0018] 根据本发明第二方面实施例的锂空气电池的制作方法,通过在空气正极的邻近有机电解液的一侧表面上设置固体电解质层,可以防止有机电解液向空气中挥发,同时抑制空气中的水分进入锂空气电池内部,从而使得锂空气电池能在敞开的工作环境中稳定工作。 [0018] According to a second aspect of the manufacturing method of the present invention, a lithium air battery of the embodiment, by providing the solid electrolyte layer on one surface adjacent the air cathode of the organic electrolyte solution, an organic electrolyte solution can be prevented from volatilization into the air while suppressing moisture in the air into the interior of lithium-air batteries, lithium air battery so that the stable operation in an open work environment.

[0019] 另外,根据本发明上述实施例的锂空气电池的制作方法还可以具有如下附加的技术特征: [0019] Further, according to the manufacturing method of a lithium air battery of the above-described embodiments of the present invention may also have the following additional technical features:

[0020] 根据本发明的一个实施例,所述步骤a)包括:a_l)提供多孔铝箔基底;a_2)对所述多孔铝箔基底进行清洗并干燥;a_3)从所述多孔铝箔基底上引出正极引出线;以及a-4)在所述多孔铝箔基底上设置氧催化剂层,得到空气正极。 [0020] According to an embodiment of the present invention, said step a) comprises: providing a porous aluminum foil substrate a_l); a_2) of the porous aluminum foil substrate was washed and dried; A_3) a positive electrode lead drawn from the porous aluminum foil substrate line; and a-4) with the oxygen in the catalyst layer on the porous aluminum foil substrate, air to obtain a positive electrode.

[0021] 根据本发明的一个实施例,在步骤a_2)中,对所述多孔铝箔基底用丙酮进行清洗后再使用蒸馏水清洗3-5次。 [0021] According to one embodiment of the present invention, in step A_2), using distilled water, the substrate was washed with porous aluminum foil and then washed 3-5 times with acetone.

[0022] 根据本发明的一个实施例,在步骤a_3)中,在所述多孔铝箔基底上焊接镍片作为正极引出线。 [0022] According to one embodiment of the present invention, in step A_3), porous aluminum foil on the base sheet as a positive electrode lead of nickel was welded.

[0023] 根据本发明的一个实施例,步骤a_4)包括:将多孔碳和氧催化剂材料混合均匀后以乙烯氰作为溶解质与PEO型高分子锂电解液混合以制备氧催化剂混合物,将所述氧催化剂混合物旋转涂抹在所述多孔铝箔基底的表面上并干燥,以在所述多孔铝箔的表面设置氧催化剂层。 [0023] According to one embodiment of the present invention, the step of A_4) comprising: after the porous carbon material and oxygen mixed catalyst mixture as ethylene cyanide dissolved substance and PEO type polymer electrolyte to prepare a lithium oxide catalyst mixture, the oxygen catalyst mixture applied on the rotating surface of the porous aluminum foil substrate and dried, to set the oxygen on the catalyst layer surface of the porous aluminum foil.

[0024] 根据本发明的一个实施例,所述氧催化剂材料为钼纳米颗粒,金纳米颗粒,a -MnO2纳米颗粒,β -MnO2纳米颗粒,Y -MnO2纳米颗粒,MoN纳米颗粒,MnN纳米颗粒,三元金属氮化物中的一种或几种。 [0024] According to an embodiment of the present invention, the material is molybdenum oxide catalyst nanoparticles, gold nanoparticles, a -MnO2 nanoparticles, β -MnO2 nanoparticles, Y -MnO2 nanoparticles, MoN nanoparticles, nanoparticles MnN ternary metal nitride of one or more.

[0025] 根据本发明的一个实施例,所述氧催化剂层中氧催化剂材料的质量含量为氧化剂层总质量的5%以下。 [0025] According to one embodiment of the present invention, the oxygen mass content of the catalyst material of the catalyst layer, the oxygen is 5% or less of the total mass of the oxidizing agent layer.

[0026] 根据本发明的一个实施例,步骤b)包括:在氮气气氛中通过溅射法、电阻加热蒸镀法、电阻束蒸镀法、电子束蒸镀法、激光磨损法中的一种在设置有氧催化剂层的多孔铝箔的表面沉积固体电解质层。 [0026] According to one embodiment of the present invention, step b) embodiment comprising: a sputtering method, resistance heating deposition method in a nitrogen atmosphere, a resistance beam deposition method, an electron beam deposition method of a medium, a laser abrasion method a solid electrolyte layer provided on the surface of the catalyst layer is porous aluminum foil oxygen deposition.

[0027] 根据本发明的一个实施例,所述固体电解质由掺杂有过渡金属元素的氮化磷酸锂构成,所述过渡金属元素包括T1、V、Cr、Mn、Fe、Co、N1、Cu、Zr、Nb、Mo、Ru、Ag、Ta、W、Pt 及Au中的一种或多种。 [0027] According to an embodiment of the present invention, the solid electrolyte is lithium nitride doped with a transition metal element constituting the phosphoric acid, the transition metal element include T1, V, Cr, Mn, Fe, Co, N1, Cu , Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au in one or more.

[0028] 根据本发明的一个实施例,在所述掺杂有过渡金属元素的氮化磷酸锂中,所述过渡金属兀素的含有率相对于磷原子为1-50原子%。 The content of [0028] According to an embodiment of the present invention, the doped lithium transition metal phosphate with a nitride of the transition metal element Wu phosphorus atom with respect to 1 to 50 atomic%. [0029] 根据本发明的一个实施例,在所述空气正极上同时射频溅射Li3PO4靶子和金属Pt靶子以得到由Ι^2.8Ρ03.45Να3ΡΤα2构成的所述固体电解质层。 [0029] According to one embodiment of the present invention, in the air while on the positive electrode Li3PO4 target RF magnetron sputtering Pt metal target and the solid electrolyte layer to obtain a Ι ^ 2.8Ρ03.45Να3ΡΤα2 configuration.

[0030] 本发明的附加方面和优点将在下面的描述中部分给出,部分将从下面的描述中变得明显,或通过本发明的实践了解到。 [0030] Additional aspects and advantages of the invention will be set forth in part in the description which follows, from the following description in part be apparent from, or learned by practice of the present invention.

附图说明 BRIEF DESCRIPTION

[0031] 本发明的上述和/或附加的方面和优点从结合下面附图对实施例的描述中将变得明显和容易理解,其中: [0031] The foregoing and / or other aspects and advantages of the invention will be described with reference to embodiments in conjunction with the embodiments become apparent and more readily appreciated below, wherein:

[0032] 图1是根据本发明实施例的锂空气电池的制作方法流程图;和 [0032] FIG. 1 is a flowchart of a method for manufacturing a lithium air battery of the present embodiment of the invention; and

[0033] 图2是根据本发明实施例的锂空气电池的结构示意图。 [0033] FIG. 2 is a diagram showing the structure of a lithium air battery according to an embodiment of the present invention.

具体实施方式 Detailed ways

[0034] 下面详细描述本发明的实施例,所述实施例的示例在附图中示出,其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。 [0034] Example embodiments of the present invention is described in detail below, exemplary embodiments of the embodiment shown in the accompanying drawings, wherein same or similar reference numerals designate the same or similar elements or elements having the same or similar functions. 下面通过参考附图描述的实施例是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。 By following with reference to the embodiments described are exemplary only for explaining the present invention and should not be construed as limiting the present invention.

[0035] 在本发明的描述中,术语“第一”、“第二”仅用于描述目的,而不能理解为指示或暗示相对重要性。 [0035] In the description of the present invention, the terms "first", "second" are used for descriptive purposes only, not to be construed to indicate or imply relative importance.

[0036] 在本发明的描述中,需要说明的是,除非另有明确的规定和限定,术语“安装”、“相连”、“连接”应做广义理解,例如,可以是固定连接,也可以是可拆卸连接,或一体地连接;可以是机械连接,也可以是电连接;可以是直接相连,也可以通过中间媒介间接相连,可以是两个元件内部的连通。 [0036] In the description of the present invention, it is noted that, unless otherwise expressly specified or limited, the terms "mounted," "connected to", "connected" are to be broadly understood, for example, may be a fixed connection, may be a detachable connection, or integrally connected; may be a mechanical connector may be electrically connected; may be directly connected, can also be connected indirectly through intervening structures, it may be in communication the interior of the two elements. 对于本领域的普通技术人员而言,可以具体情况理解上述术语在本发明中的具体含义。 Those of ordinary skill in the art, be appreciated that the specific circumstances of the specific meanings in the present invention.

[0037] 下面参考图1描述根据本发明的实施例的锂空气电池的制作方法。 [0037] FIG. 1 is described below with reference to the production method of a lithium air battery of the embodiment of the present invention.

[0038] a)提供空气正极。 [0038] a) providing positive air.

[0039] 关于空气正极没有特殊的限制,例如可以通过以下具体步骤提供空气正极: [0039] For the air cathode is not particularly limited, the positive electrode may be provided by the following specific steps of air:

[0040] a-1)提供多孔铝箔基底。 [0040] a-1) providing a porous aluminum foil substrate.

[0041] a-2)对多孔铝箔基底进行清洗并干燥。 [0041] a-2) of the porous aluminum foil substrate is cleaned and dried.

[0042] 在步骤a_2)中,对多孔铝箔基底的清洗时,可以用丙酮进行清洗后再使用蒸馏水清洗,例如用丙酮清洗后在用蒸馏水清洗3-5次。 [0042] In step A_2), for cleaning the porous aluminum foil substrate can be washed with acetone and then washed with distilled water, washed with acetone, for example, after washed with distilled water 3-5 times. 由此,可以对多孔铝箔清洗的更加彻底,以满足作为基底的要求。 Thereby, it is possible for more thorough cleaning porous aluminum foil, to meet the requirements as a substrate.

[0043] a_3)从多孔铝箔基底上引出正极引出线。 [0043] a_3) a positive electrode lead drawn from the porous aluminum foil substrate. 对铝箔基底清洗干燥后,在铝箔基底上引出正极引出线,由此,方便组装成电池。 After washing the aluminum foil substrate and dried, the positive electrode lead drawn on an aluminum foil substrate, thereby easily assembled into a battery.

[0044] 优选地,在步骤a_3)中,可以在多孔铝箔基底上焊接镍片作为正极引出线。 [0044] Preferably, in step A_3), an aluminum foil on the porous substrate may be a nickel plate as a positive electrode lead welding.

[0045] a-4)在多孔铝箔基底上设置氧催化剂层,设置氧催化剂层后就得到需要的空气正极。 [0045] a-4) a catalyst layer provided on the porous oxide aluminum substrate, the catalyst layer after the oxygen is provided to obtain desired air cathode.

[0046] 具体地,步骤a_4)中可以包括:将多孔碳和氧催化剂材料混合均匀后以乙烯氰作为溶解质与PEO型高分子锂电解液混合以制备氧催化剂混合物,将所述氧催化剂混合物旋转涂抹在所述多孔铝箔基底的表面上并干燥,以在多孔铝箔的表面设置氧催化剂层。 [0046] Specifically, in step A_4) may include: carbon and oxygen after the porous catalyst material mixed ethylene cyanide dissolved as a mixed substance and PEO type polymer electrolyte to prepare a lithium oxide catalyst mixture, the catalyst mixture of the oxygen rotation applied on the surface of the porous aluminum foil substrate and dried, the oxygen is provided to the catalyst layer on the surface of the porous aluminum foil.

[0047] 氧催化剂材料可以为钼纳米颗粒,金纳米颗粒,a-MnO2纳米颗粒,β-MnO2纳米颗粒,Y -MnO2纳米颗粒,MoN纳米颗粒,MnN纳米颗粒,三元金属氮化物中的一种或几种。 [0047] The catalyst material may be a molybdenum oxide nanoparticles, gold nanoparticles, a-MnO2 nanoparticles, β-MnO2 nanoparticles, Y -MnO2 nanoparticles, MoN nanoparticles, nanoparticles MnN, ternary metal nitrides in a one or several.

[0048] 氧催化剂层中氧催化剂材料的质量含量可以为氧催化剂层总质量的5%以下。 [0048] The oxygen content of the oxygen mass in the catalyst layer of the catalyst material be 5% of the total mass of the catalyst layer is less oxygen. b)在空气正极的表面上沉积固体电解质层。 b) a solid electrolyte layer is deposited on the surface of the air cathode.

[0049] 具体地,可以在氮气气氛中通过溅射法、电阻加热蒸镀法、电阻束蒸镀法、电子束蒸镀法、激光磨损法中的一种在设置有氧催化剂层的多孔铝箔的表面沉积固体电解质层。 [0049] In particular, by a sputtering method, resistance heating deposition method in a nitrogen atmosphere, a resistance beam deposition method, an electron beam evaporation method, a laser ablation method in which the oxygen in the catalyst layer is porous aluminum foil deposited on the surface of the solid electrolyte layer.

[0050] 其中,固体电解质由掺杂有过渡金属元素的氮化磷酸锂构成,所述过渡金属元素包括T1、V、Cr、Mn、Fe、Co、N1、Cu、Zr、Nb、Mo、Ru、Ag、Ta、W、Pt 及Au 中的一种或多种。 [0050] wherein the solid electrolyte is doped with transition metal elements constituting the lithium phosphate nitride, a transition metal element include T1, V, Cr, Mn, Fe, Co, N1, Cu, Zr, Nb, Mo, Ru , Ag, Ta, W, Pt and Au in one or more.

[0051] 优选地,在掺杂有过渡金属元素的氮化磷酸锂中,过渡金属元素的含有率相对于憐原子为1_50原子%。 [0051] Preferably, the lithium phosphate nitride doped with a transition metal element, the content of transition metal elements with respect to Rei atom 1_50 atomic%.

[0052] 例如,可以在空气正极上同时射频溅射Li3PO4靶子和金属Pt靶子以得到由Li2.8P03.45N0.3PT0.2构成的固体电解质层。 [0052] For example, while Li3PO4 target RF magnetron sputtering target and Pt metal on the cathode air to obtain a solid electrolyte layer made of Li2.8P03.45N0.3PT0.2 thereof.

[0053] c)将沉积有固体电解质层的空气正极、有机电解液以及锂负极依序装配成锂空气电池,其中所述空气电极的沉积有固体电解质层一侧表面与所述有机电解液相邻。 [0053] c) depositing a solid electrolyte layer of the air cathode of the organic electrolyte and a lithium negative electrode are sequentially assembled into a lithium-air battery, wherein said air electrode is deposited with a side surface of the solid electrolyte layer and the organic electrolyte phase adjacent.

[0054] 在空气正极上沉积固体电解质层后,将沉积有固体电解质层的空气正极、有机电解液以及锂负极依序装配成锂空气电池。 [0054] After deposition of the solid electrolyte layer on the positive electrode in the air, the air cathode is deposited solid electrolyte layer, an organic electrolyte and a lithium negative electrode are sequentially assembled into a lithium-air battery.

[0055] 由此,如图2所示,通过上述制备方法制得锂空气电池可以包括:空气正极1、锂负极4以及填充在空气电极I和锂负极4之间的有机电解液3。 [0055] Accordingly, as shown in Figure 2, by the above production method can produce the lithium air battery comprising: a positive electrode 1 of air, a negative electrode 4, and the lithium negative electrode is filled in the air electrode I and a lithium organic electrolyte between 43. 其中,在空气正极I的邻近有机电解液3的一侧表面11上设置有固体电解质层2。 Wherein, in the organic electrolyte solution air adjacent the side I of the positive electrode 3 is provided with a surface 11 of the solid electrolyte layer 2.

[0056] 根据上述方法制得的锂空气电池,通过在空气正极I的邻近有机电解液3的一侧表面上设置固体电解质层2,可以防止有机电解液3通过空气电极I而向空气中挥发,同时抑制空气中的水分通过空气电极I而进入锂空气电池内部,从而使得锂空气电池能在敞开的工作环境中稳定工作。 [0056] According to the method described above prepared lithium air batteries, by providing a solid electrolyte layer on one side surface adjacent the air cathode organic electrolyte solution of I 3 2, 3 can be prevented volatilized organic electrolyte through the air to the air electrode I while suppressing moisture in the air through the air electrode I into the interior of lithium-air batteries, lithium air battery so that the stable operation in an open work environment.

[0057] 根据本发明的一些实施例,空气正极I包括金属铝箔12和形成于金属铝箔12上的氧催化剂层(未示出)。 [0057] According to some embodiments of the present invention, the positive electrode comprises a metal foil 12 I air and oxygen catalyst layer (not shown) formed on the metal foil 12. 金属铝箔12在锂空气电池中可以作为正极集流体,其上形成有氧催化剂层,可以克服空气中氧还原过程中的电化学极化,使电池的效率提高。 Metal foil 12 in the lithium-air battery can be used as a positive electrode current collector, a catalyst layer formed thereon oxygen, air electrochemical polarization can be overcome in the process of oxygen reduction in the efficiency of the battery.

[0058] 进一步地,氧催化剂层由载体,例如为多孔碳,和氧催化剂材料形成,氧催化剂材料选自钼纳米颗粒、金纳米颗粒、ct -MnO2纳米颗粒、β -MnO2纳米颗粒、Y -MnO2纳米颗粒、MoN纳米颗粒、MnN纳米颗粒、三元金属氮化物中的一种或几种材料形成。 [0058] Further, the oxygen of the catalyst layer, for example, porous carbon, and oxygen catalyst material is formed by the carrier, the catalyst material is selected from molybdenum oxide nanoparticles, gold nanoparticles, ct -MnO2 nanoparticles, β -MnO2 nanoparticles, Y - MnO2 nanoparticles, MoN nanoparticles, nanoparticles MnN, ternary metal nitrides of one or more materials. 由此,氧催化剂材料采用上述材料的一种或多种形成可以使氧催化剂层的催化效率更高。 Accordingly, the oxygen of the catalyst materials using one of the above materials or more oxygen can form higher catalytic efficiency of the catalyst layer.

[0059] 可选地,所述氧催化剂层中氧催化剂材料的质量含量为为氧催化剂层总质量的5%以下。 [0059] Alternatively, the oxygen mass content of the catalyst material of the catalyst layer of the oxygen is 5% of the total mass of the catalyst layer is less oxygen. 由此,可以节约生产成本,并将氧催化剂层的催化效果控制在较好的范围内。 Accordingly, the production cost can be saved, and the catalytic effect of the oxygen in the catalyst layer is controlled within a preferred range.

[0060] 根据本发明的一个实施例,固体电解质层2由掺杂有过渡金属元素的氮化磷酸锂构成,过渡金属元素包括T1、V、Cr、Mn、Fe、Co、N1、Cu、Zr、Nb、Mo、Ru、Ag、Ta、W、Pt 及Au 中的一种或多种。 [0060] According to one embodiment of the present invention, the solid electrolyte layer 2 doped lithium transition metal phosphate nitride constituting elements, transition metal elements including T1, V, Cr, Mn, Fe, Co, N1, Cu, Zr , Nb, Mo, Ru, Ag, Ta, W, Pt and Au in one or more. 由此,形成的固体电解质层2可以防止有机电解液3向空气中挥发,同时抑制空气中的水分进入锂空气电池内部,即防止空气中的水分进入有机电解液3中,从而使得锂空气电池能在敞开的工作环境中稳定工作。 Thus, the solid electrolyte layer 2 can be prevented from forming volatile organic electrolytic solution 3 into the air while suppressing moisture in the air into the interior of lithium-air battery, i.e., to prevent moisture in the air into the organic electrolytic solution 3, so that the lithium air battery stable operation in an open work environment.

[0061] 进一步地,在掺杂有过渡金属元素的氮化磷酸锂中,过渡金属元素的含有率相对于磷原子为1-50原子%。 [0061] Further, the lithium phosphate nitride doped with a transition metal element, a transition metal element content of phosphorus atoms relative to 1 to 50 atomic%. 由此,可以使固体电解质层2的隔离水分的效果更好。 Thus, the effect of the solid electrolyte layer can be made of 2 better moisture separator.

[0062] 例如,在本发明的一个实施例中,固体电解质层2可以由Ι^2.8Ρ03.45Να3ΡΤα2构成。 [0062] For example, in one embodiment of the present invention, the solid electrolyte layer 2 may be constituted by Ι ^ 2.8Ρ03.45Να3ΡΤα2. [0063] 根据本发明的一些示例,固体电解质层2的厚度可以为O. 1-0. 2微米。 [0063] According to some examples of the present invention, the thickness of the solid electrolyte layer 2 may be O. 1-0. 2 microns. 由此,可以方便锂空气电池的加工,制作起来更加方便。 This can facilitate the processing of a lithium air battery, making it more convenient.

[0064] 下面通过具体实施例描述本发明的锂空气电池的制作方法。 [0064] The following specific embodiments of the method for manufacturing lithium air battery according to the present invention will be described.

[0065] 实施例1 [0065] Example 1

[0066] 将多孔铝箔用丙酮进行清洗,然后用蒸馏水清洗3-5次,烘干,制作成基底;然后在基底上焊接一个镍片作正极弓I出线。 [0066] The porous aluminum foil was washed with acetone, then washed 3-5 times with distilled water, dried, made into a substrate; then welding a positive electrode for a nickel sheet I bow line on the substrate.

[0067] 将多孔碳和a-MnO2纳米颗粒按照质量比为95% : 5%混合均匀,然后加入5%质量的PEO型高分子锂电解液混合,用乙烯氰作为溶解质,旋转涂抹在上述多基底上烘干,得到锂离子空气电池的空气正极。 [0067] The porous carbon and a-MnO2 nanoparticles a mass ratio of 95%: Lithium PEO type polymer electrolyte mixture 5% mixed, followed by addition of 5% by mass, with ethylene as the cyanide dissolved substance, applied in the above-described rotation multi the substrate drying air to obtain a positive electrode of a lithium ion battery air.

[0068] 在氮气气氛中,在基底的薄膜上同时射频溅射Li3PO4靶子和金属钛靶子,控制溅射速率,使得沉积产物化学式Ι^2.8Ρ03.45Να3ΡΤα2,厚度O. 1-0. 2 μ m,从而在空气正极上沉积·形成固体电解质层。 [0068] In a nitrogen atmosphere, while Li3PO4 target RF magnetron sputtering target of titanium metal and the substrate on the film, the sputtering rate is controlled so that the deposition product of Formula Ι ^ 2.8Ρ03.45Να3ΡΤα2, thickness O. 1-0. 2 μ m , whereby the positive electrode is deposited on an air-formed solid electrolyte layer.

[0069] 将沉积有所述固体电解质层的空气正极、金属锂负极以及有机电解液组装成电池。 [0069] The air cathode deposited layer of the solid electrolyte, lithium metal negative electrode and an organic electrolyte battery was assembled.

[0070] 实施例2 [0070] Example 2

[0071] 将多孔铝箔用丙酮进行清洗,然后用蒸馏水清洗3-5次,烘干,制作成基底;然后在基底上焊接一个镍片作正极引出线; [0071] The porous aluminum foil was washed with acetone, then washed 3-5 times with distilled water, dried, made into a substrate; the substrate is then welded on a nickel plate as a positive electrode lead;

[0072] 将多孔碳和钼纳米颗粒按照质量比为95% : 5%混合均匀,然后加入5%质量的PEO型高分子锂电解液混合,用乙烯氰作为溶解质,旋转涂抹在上述基底上烘干,得到锂离子空气电池的空气正极。 [0072] The porous carbon nanoparticles and the mass ratio of molybdenum was 95%: Lithium PEO type polymer electrolyte mixture 5% mixed, followed by addition of 5% by mass, with ethylene as the cyanide dissolved substance, the applicator on the base rotating drying air to obtain a positive electrode of a lithium ion battery air.

[0073] 在氮气气氛中,在基底薄膜上同时射频溅射Li3PO4靶子和金属Pt靶子,控制溅射速率,使得沉积产物化学式Ι^2.8Ρ03.45Να3ΡΤα2,厚度O. 1-0. 2 μ m,从而在空气正极上沉积形成固体电解质层。 [0073] In a nitrogen atmosphere, while the film on the substrate by RF magnetron sputtering target and Li3PO4 Pt metal target, the sputtering rate is controlled so that the deposition product of Formula Ι ^ 2.8Ρ03.45Να3ΡΤα2, thickness O. 1-0. 2 μ m, thereby depositing a solid electrolyte layer on the cathode air.

[0074] 将沉积有所述固体电解质层的空气正极、金属锂负极以及有机电解液组装成电池。 [0074] The air cathode deposited layer of the solid electrolyte, lithium metal negative electrode and an organic electrolyte battery was assembled.

[0075] 在本说明书的描述中,参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。 [0075] In the description of the present specification, reference to the term "one embodiment," "some embodiments", "an example", "a specific example", or "some examples" means that a description of the exemplary embodiment or embodiments described a particular feature, structure, material, or characteristic is included in at least one embodiment of the present invention, embodiments or examples. 在本说明书中,对上述术语的示意性表述不一定指的是相同的实施例或示例。 In the present specification, a schematic representation of the above terms necessarily referring to the same embodiment or example. 而且,描述的具体特征、结构、材料或者特点可以在任何的一个或多个实施例或示例中以合适的方式结合。 Furthermore, the particular features, structures, materials, or characteristics described embodiments or examples may be at any one or more in a proper manner.

[0076] 尽管已经示出和描述了本发明的实施例,本领域的普通技术人员可以理解:在不脱离本发明的原理和宗旨的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由权利要求及其等同物限定。 [0076] While there has been illustrated and described embodiments of the present invention, those of ordinary skill in the art can be appreciated: that various changes may be made to these embodiments without departing from the principles and spirit of the invention, modifications, substitutions and modifications, the scope of the present invention is defined by the claims and their equivalents.

Claims (19)

1. 一种锂空气电池,其特征在于,包括空气正极、锂负极以及填充在所述空气电极和锂负极之间的有机电解液,其中,在所述空气电极的邻近所述有机电解液的一侧表面上设置有固体电解质层。 A lithium-air battery comprising an air cathode, a lithium negative electrode, and filled between the air electrode and the negative electrode of a lithium organic electrolyte, wherein adjacent to the air electrode of the organic electrolyte solution It is provided with a solid electrolyte layer on one surface.
2.根据权利要求1所述的锂空气电池,其特征在于,所述空气正极包括金属铝箔和形成于所述金属铝箔上的氧催化剂层。 The lithium air battery according to claim 1, wherein said positive electrode comprises a metal foil and air oxygen is formed on the catalyst layer of metal foil.
3.根据权利要求2所述的锂空气电池,其特征在于,所述氧催化剂层由载体和氧催化剂材料形成,所述氧催化剂材料选自钼纳米颗粒、金纳米颗粒、Ct-MnO2纳米颗粒、β-MnO2 纳米颗粒、Y -MnO2纳米颗粒、MoN纳米颗粒、MnN纳米颗粒、三元金属氮化物中的一种或几种。 3. The lithium air battery according to claim 2, wherein said catalyst layer is formed of an oxygen carrier oxygen and a catalyst material, said catalyst material is selected from molybdenum oxide nanoparticles, gold nanoparticles, Ct-MnO2 nanoparticles , β-MnO2 nanoparticles, Y -MnO2 nanoparticles, MoN nanoparticles, nanoparticles MnN, ternary metal nitrides of one or more.
4.根据权利要求3所述的锂空气电池,其特征在于,所述氧催化剂层中氧催化剂材料的质量含量为为氧催化剂层总质量的5%以下。 4. The lithium air battery according to claim 3, wherein the oxygen mass content of the catalyst material of the catalyst layer of the oxygen is 5% of the total mass of the catalyst layer is less oxygen.
5.根据权利要求1所述的锂空气电池,其特征在于,所述固体电解质层由掺杂有过渡金属元素的氮化磷酸锂构成,所述过渡金属元素包括T1、V、Cr、Mn、Fe、Co、N1、Cu、Zr、Nb、 Mo、Ru、Ag、Ta、W、Pt及Au中的一种或多种。 The lithium air battery according to claim 1, wherein said solid electrolyte layer is doped with a transition metal nitride, lithium phosphate element constituting the transition metal element include T1, V, Cr, Mn, Fe, Co, N1, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt, and one or more of Au.
6.根据权利要求5所述的锂空气电池,其特征在于,在所述掺杂有过渡金属元素的氮化磷酸锂中,所述过渡金属元素的含有率相对于磷原子为1-50原子%。 6. The lithium air battery according to claim 5, characterized in that the doped lithium transition metal phosphate nitride element, the content of the transition metal element with respect to the phosphorus atom of 1 to 50 atoms %.
7.根据权利要求5所述的锂空气电池,其特征在于,所述固体电解质层由Li2.8P03.45NQ.3PT0.2 构成。 7. The lithium air battery according to claim 5, wherein said solid electrolyte layer is made Li2.8P03.45NQ.3PT0.2.
8.根据权利要求5所述的锂空气电池,其特征在于,所述固体电解质层的厚度为O. 1-0. 2 微米。 8. The lithium air battery according to claim 5, wherein a thickness of the solid electrolyte layer is O. 1-0. 2 microns.
9. 一种锂空气电池的制作方法,其特征在于,包括以下步骤:a)提供空气正极;b)在所述空气正极的表面上沉积固体电解质层;以及c)将沉积有所述固体电解质层的空气正极、有机电解液以及锂负极依序装配成锂空气电池,其中所述空气电极的沉积有固体电解质层一侧表面与所述有机电解液相邻。 A manufacturing method of a lithium air battery, characterized by comprising the steps of: a) providing a positive air; b) depositing a solid electrolyte layer on the surface of the air cathode; and c) depositing the solid electrolyte has an air cathode layer, an organic electrolyte and a lithium negative electrode are sequentially assembled into a lithium-air battery, wherein said air electrode is deposited with a side surface of the solid electrolyte layer adjacent to the organic electrolytic solution.
10.根据权利要求9所述的锂空气电池的制作方法,其特征在于,所述步骤a)包括:a-Ι)提供多孔铝箔基底;a-2)对所述多孔铝箔基底进行清洗并干燥;a-3)从所述多孔铝箔基底上引出正极引出线;以及a-4)在所述多孔铝箔基底上设置氧催化剂层,得到空气正极。 10. A manufacturing method of a lithium air battery according to claim 9, wherein said step a) comprises: a-Ι) providing a porous aluminum foil substrate; a-2) of the porous aluminum foil substrate is cleaned and dried ; a-3) a positive electrode lead drawn from an aluminum foil on the porous substrate; and a-4) with the oxygen in the catalyst layer on the porous aluminum foil substrate, air to obtain a positive electrode.
11.根据权利要求10所述的锂空气电池的制作方法,其特征在于,在步骤a-2)中,对所述多孔铝箔基底用丙酮进行清洗后再使用蒸馏水清洗3-5次。 11. A manufacturing method of a lithium air battery according to claim 10, wherein, in a) in step a-2, using distilled water, the substrate was washed with porous aluminum foil and then washed 3-5 times with acetone.
12.根据权利要求10所述的锂空气电池的制作方法,其特征在于,在步骤a-3)中,在所述多孔铝箔基底上焊接镍片作为正极引出线。 12. A manufacturing method of a lithium air battery according to claim 10, wherein, in step a-3), an aluminum foil on said porous substrate sheet as a positive electrode lead of nickel was welded.
13.根据权利要求10所述的锂空气电池的制作方法,其特征在于,步骤a-4)包括:将多孔碳和氧催化剂材料混合均匀后以乙烯氰作为溶解质与PEO型高分子锂电解液混合以制备氧催化剂混合物,将所述氧催化剂混合物旋转涂抹在所述多孔铝箔基底的表面上并干燥,以在所述多孔铝箔的表面设置氧催化剂层。 13. A manufacturing method of a lithium air battery according to claim 10, wherein step a-4) comprising: after the porous carbon material and oxygen mixed catalyst as ethylene cyanide dissolved substance and PEO type polymer lithium solution the catalyst mixture prepared was mixed to oxygen, the oxygen of the catalyst mixture was applied on the rotating surface of the porous aluminum foil substrate and dried, to set the oxygen on the catalyst layer surface of the porous aluminum foil.
14.根据权利要求13所述的锂空气电池的制作方法,其特征在于,所述氧催化剂材料为钼纳米颗粒,金纳米颗粒,a -MnO2纳米颗粒,β -MnO2纳米颗粒,Y -MnO2纳米颗粒,MoN纳米颗粒,MnN纳米颗粒,三元金属氮化物中的一种或几种。 14. The manufacturing method of the lithium air battery of claim 13, characterized in that said material is molybdenum oxide catalyst nanoparticles, gold nanoparticles, a -MnO2 nanoparticles, β -MnO2 nanoparticles, Y -MnO2 nano particles, MoN nanoparticles, nanoparticles MnN, ternary metal nitrides of one or more.
15.根据权利要求13所述的锂空气电池的制作方法,其特征在于,所述氧催化剂层中氧催化剂材料的质量含量为氧化剂层总质量的5%以下。 15. The method of claim 13 making a lithium air battery according to claim, wherein the mass content of the oxygen-oxygen catalyst material of the catalyst layer is 5% or less of the total mass of the oxidizing agent layer.
16.根据权利要求9所述的锂空气电池的制作方法,其特征在于,步骤b)包括: 在氮气气氛中通过溅射法、电阻加热蒸镀法、电阻束蒸镀法、电子束蒸镀法、激光磨损法中的一种在设置有氧催化剂层的多孔铝箔的表面沉积固体电解质层。 16. The manufacturing method of a lithium air battery according to claim 9, wherein step b) comprises: by a sputtering method, resistance heating deposition method in a nitrogen atmosphere, a resistance beam deposition, electron beam evaporation method a method of laser ablation is deposited on the surface of the solid electrolyte layer is provided a porous oxygen catalyst layer of aluminum foil.
17.根据权利要求16所述的锂空气电池的制作方法,其特征在于,所述固体电解质由掺杂有过渡金属元素的氮化磷酸锂构成,所述过渡金属元素包括T1、V、Cr、Mn、Fe、Co、N1、 Cu、Zr、Nb、Mo、Ru、Ag、Ta、W、Pt 及Au 中的一种或多种。 17. The method of claim 16 making a lithium air battery according to claim, characterized in that the solid electrolyte is lithium nitride doped with a transition metal element constituting the phosphoric acid, the transition metal element include T1, V, Cr, mn, Fe, Co, N1, Cu, Zr, Nb, Mo, Ru, Ag, Ta, W, Pt and Au in one or more.
18.根据权利要求17所述的锂空气电池的制作方法,其特征在于,在所述掺杂有过渡金属元素的氮化磷酸锂中,所述过渡金属元素的含有率相对于磷原子为1-50原子%。 18. A manufacturing method of a lithium air battery according to claim 17, wherein the doped phosphate with a lithium nitride of a transition metal element, the content of the transition metal element with respect to the phosphorus atom is 1 -50 atom%.
19.根据权利要求17所述的锂空气电池的制作方法,其特征在于,在所述空气正极上同时射频溅射Li3PO4靶子和金属Pt靶子以得到由Li2.8P03.4具.3ΡΤα2构成的所述固体电解质层。 19. The method of claim 17 making a lithium air battery according to claim, wherein the RF magnetron sputtering while the Pt metal target and Li3PO4 target in the air on the positive electrode is made of Li2.8P03.4 obtained having .3ΡΤα2 said solid electrolyte layer.
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